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Biomass screening for syngas production by flash

Cite this: RSC Adv., 2024, 14, 11706
photopyrolysis†
Open Access Article. Published on 11 April 2024. Downloaded on 5/1/2024 11:35:31 AM.
Abderrahman Mellalou, a Wanderson O. Silva, b Mathieu Soutrenon, b
Hubert H. Girault, c Abdelkader Outzourhit,d Jones Alamia

and Fouad Ghamouss *a
A few seconds flash photopyrolysis is used as efficient screening tool for the investigation of selected
biomass in producing syngas, hydrogen and biochar. This innovative approach allowed rapid pyrolysis of
the biomass, which was followed by a precise gas analysis and quantification, using Mass Spectrometry
(MS). The analysis of the gas composition from three distinct biomass wastes in this study provides new
Received 10th March 2024
Accepted 6th April 2024
insights into their thermochemical characteristics, expanding thus our knowledge of the potential of the
selected biomass resources for the production of carbon, syngas, and/or hydrogen-rich gas production.
DOI: 10.1039/d4ra01845a
This enhanced characterization revealed the potential of biomass transformation in contributing to
rsc.li/rsc-advances innovative green energy sustainable solutions.
emission-free utilization is promising in the reduction of air

Introduction pollutants and greenhouse gas emissions, thereby contributing
Biomass is a readily accessible and abundantly available to the attenuation of the environmental effects associated with
renewable energy resource on Earth, and may play a major role traditional fossil fuels. Indeed, the viability of hydrogen as
in the sustainable energy production landscape.1 Globally a pivotal element in the transition to a cleaner energy has been
recognized as the fourth most abundant energy resource, justied through extensive research and experimentation.5,6,8 Its
biomass contributes to over 10% of the total energy supply.2 application in industries spanning transportation, power
Biomass research has recently attracted growing attention, generation, and industrial processes highlights its potential to
driven by the evident potential of waste-to-energy conversion.3 revolutionize the way energy is sourced and utilized.9 Moreover,
Biomass can be primarily used to produce electricity/heat ongoing advancements in hydrogen production, storage, and
energy, transport fuels and synthetic hydrogen-rich gas distribution technologies further solidify its position as
commonly known as syngas,4 composed primarily of CO and a pivotal energy vector for the future.
H2. In addition to its direct use as a fuel in power generation Syngas or hydrogen rich-gas stands out as a versatile precursor
and transportation, syngas is also a potential feedstock for for various industrial applications, serving as a vital raw material
chemical production.5 Notably, about 50% of the total syngas for synthesizing fuels, chemicals, and fertilizers. Its signicance
produced is directed towards ammonia production, with an lies in its potential to mitigate carbon emissions by enabling the
additional 25% dedicated to hydrogen production.6 The production of clean fuels and chemicals from renewable
remaining portion is used in the production of methanol and resources. Syngas gas can be derived from diverse primary energy
hydrocarbons, exemplied by processes such as Fischer– sources, including coal, natural gas and biomass.5 Primary, non-
Tropsch synthesis.7 renewable and GHG emitting feedstock, namely, coal and
Hydrogen is recognized as one of the most versatile energy petroleum residues together with coke are the main raw mate-
carriers, as it is demonstrated to meet a wide range of energy rials traditionally used in gasication and steam reforming
needs across various sectors.8 Its inherent potential for processes for syngas production.10 However, the urgent need for
the transition towards a circular economy has boosted the search
for carbon neutral, highly efficient, environmentally friendly, and
a
Materials Science Energy and Nanoengineering Department, Mohamed VI Polytechnic
sustainable alternatives. Biomass is recognized as a renewable
University, Benguerir, Morocco. E-mail: [email protected]
b
and sustainable source for producing syngas. This can be ach-
Institute of Systems Engineering, HES-SO Valais-Wallis, CH-1950 Sion, Switzerland
c
Institut des Sciences et Ingénierie Chimiques (ISIC), École Polytechnique Fédérale de
ieved primarily through thermochemical methods such as
Lausanne (EPFL), Station 6, CH-1015 Lausanne, Switzerland pyrolysis and gasication, as well as biological techniques like
d
Laboratory of Materials, Energy and Environment, Faculty of Sciences Semlalia, Cadi fermentation and anaerobic digestion.11
Ayyad University, Morocco There is a variety of biomass feedstocks that emanate from
† Electronic supplementary information (ESI) available. See DOI: organic wastes such as agricultural crop residues, wood,
https://doi.org/10.1039/d4ra01845a
11706 | RSC Adv., 2024, 14, 11706–11714 © 2024 The Author(s). Published by the Royal Society of Chemistry
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municipal waste, and wet waste such as crop residues, forest Materials and methods
residues, algae, and various industrial byproducts, including
wastewater.12 In Morocco, the agricultural sector contributes Various biomass feedstocks were used in order to evaluate the
signicantly to organic waste production, generating approxi- potential of photo-pyrolysis as a screening tool for syngas and
mately 65 million tons per year.13 This estimate relies on residue hydrogen rich gas production.
production per hectare drawn from prior studies and research
ndings by the FAO.14 However, these ratios are subject to
various inuencing factors, including edaphic and climatic Feedstocks description
conditions, as well as cultural practices.13 The potential energy Pennisetum villosum, commonly referred to as feathertop grass
yield achievable through the utilization of this biomass and or simply feathertop, represents a owering plant belonging to
waste amounts to approximately 13 million MW h per year,
the Poaceae family, as depicted in Fig. 1a. Indigenous to

comprising 6.6 million MW h from the agricultural sector, 3.5 northeastern Africa and certain regions of the Arabian Penin-
million MW h from forestry activities, and 3.3 million MW h sula, this species is also cultivated as an ornamental plant in
from waste resources.14 various other locations. Instances of its spontaneous growth
Among the above mentioned biomass conversion methods, beyond cultivation are occasionally encountered. The plant's
thermochemical processes emerge as particularly promising inorescence is characterized by a panicle housing clustered
pathways for converting biomass into syngas.8,11 Specically, spikelets enveloped by a mist-like assembly of plumose white
pyrolysis, which involves the decomposition of biomass in the bristles, measuring up to 5 centimeters in length.
absence of oxygen, and gasication, a process that converts Pennisetum alopecuroides (Fig. 1b), a member of the grass
biomass into a gas mixture primarily composed of hydrogen, family (Poaceae), traces its origins to Africa (1913). Centuries
carbon monoxide, and carbon dioxide, have demonstrated ago, it was introduced as animal fodder across South America,
signicant potentials.15 Asia, and Australia. In Morocco, these plants thrives abun-
While pyrolysis focuses on the thermal breakdown of dantly, notably within urban areas along roadways, oen
biomass, gasication revolves around the transformation of attaining heights of up to 75 cm and 2 meters, respectively.
biomass into a gaseous form. However, an essential prerequi- Annually, substantial quantities of Pennisetum villosum and
site for demonstrating the syngas production potential and Pennisetum alopecuroides plants are generated as a byproduct of
maximizing syngas yield of biomass lies in effectively catego- public green space maintenance, oen discarded on the city's
rizing and classifying diverse biomass feedstocks. In this open surfaces or employed as fuel in traditional baths
regard, photopyrolysis emerges as a promising screening tech- (Hammams).
nique to reveal the capabilities of various biomass materials for Onions (Allium cepa L.) holds a signicant position among
syngas and hydrogen rich gas production.16 all horticultural commodities and ranks second only to toma-
Photopyrolysis is a non-thermal surface process that uses toes in terms of global production.22 Worldwide onion
high power pulsed xenon light (ms to ms) to decompose production amounts to approximately 64.5 million tons,
biomass, such as banana peel into syngas and porous carbon.16 covering an agricultural eld area of about 3.45 million ha.
Recent work demonstrated that this technique can also be used According to data from the National Horticulture Research and
to produce hydrogen from tires.17 Through the application of Development Foundation, Moroccan onion production is pro-
light pulses characterized by varying intensities and a wide jected to reach 962 680 metric tons by 2026, with an average
range of wavelengths, a succession of photo-thermal and photo- annual productivity growth rate of 0.8%.23 Furthermore, onions
chemical reactions is initiated. Originally designed for photonic stand out as one of the most export-oriented vegetable cate-
sintering, this pulsed light system saw its rst application in gories in Morocco, ranking third among the most exported
drying edge-oxidized graphene nanosheet lms for rapid vegetables. The exportation rate usually peaks during July and
establishment of a compact electrode surface.18 Another appli- August, but declines signicantly aer February. Consequently,
cation was the synthesis of molybdenum carbides (Mo2C)-based post-harvest waste (Petiole and Flower), Fig. 1c, from onions can
electrocatalysts on a carbon cloth substrate under ambient amount to a signicant quantities, averaging 0.5 kg per kg of
conditions via photonic ash synthesis (PFS) from a MoO3/
graphene precursor.19 The pulsed light treatment facilitated the
effective thermal decomposition of molybdenum oxides into
a porous b-Mo2C nanostructure with impressively high catalytic
stability. Xenon ashlamp units are, otherwise, widely used in
diverse domains including, photonic sintering,20 surface treat-
ment, food processing,21 and more.
In this context, the present research is a comprehensive
investigation of photo-pyrolysis as a screening tool to evaluate
syngas production potential of different biomass feedstocks.
More specically, photopyrolysis effectiveness to evaluate the Fig. 1 Photograph of (a) Pennisetum villosum (b) the Pennisetum
capacity of various Moroccan biomass sources to yield syngas alopecuroides and (c) the onion post-harvesting waste (Petiole and
and in particular hydrogen is demonstrated. Flower).
© 2024 The Author(s). Published by the Royal Society of Chemistry RSC Adv., 2024, 14, 11706–11714 | 11707
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produced onions. In general, onion waste can be categorized the mass obtained aer the solubility test of the bers in the
into three main types: industrial waste, domestic waste, and ethanol–toluene mixture (%).
post-harvest or supply chain waste. This waste has gained The quantication of hemicellulose content was based on
signicant attention in recent years due to its potential appli- the procedure established by Boopathi et al.27 Biomass samples
cations in various elds, ranging from agriculture to biotech- underwent immersion in a 5% NaOH solution at room
nology. However, because of its high sulfur content and strong temperature for a duration of 30 minutes, followed by neutral-
aroma, it cannot be valorized as soil amendment. Nonetheless, ization using an HCl solution. Ultimately, the bers were sub-
it contains rich reserves of ber, minerals, and bioactive jected to drying in an oven set at 105 °C for 2 hours. The
compounds that can be recovered to develop various bio- resulting change in weight from this process yielded the
products, such as bioenzymes and polyphenols.24 hemicellulose content, %hemicellulose = (m1 − m2) × 100, with
Given its abundant cellulose content, these waste materials m1 and m2 the masses of the bers before and aer treatment.
can be potentially used either as a sustainable biofuel through Each one of these experiments was repeated 5 times and the
direct combustion or as a resource for syngas or hydrogen-rich mean values were reported.
gas production via thermochemical techniques like pyrolysis The infrared spectra of raw biomass waste were recorded
and gasication. using a PerkinElmer Fourier transform infrared spectropho-
Therefore, as part of the present study, we conducted tometer in the wavenumber range 4000–400 cm−1. For this
a comprehensive chemical, and physical assessment of purpose, 2 mg of each biomass waste was ground into small
Moroccan Pennisetum alopecuroides, Pennisetum villosum and particle and mixed with KBr.
onion waste (petiole and ower) with a specic focus on its The XRD tests were performed using a Bruker D8 discover
applicability within the eld of bioenergy, notably for syngas diffractometer at 40 kV and 30 mA at room temperature. This
and hydrogen rich-gas generation. system has a rotating anode generator with a copper target
All samples were collected in the Marrakech region during radiation source (l = 1.5406 Å). The (2q) angle was scanned
the spring season, subsequently ground to ner particles before between 5° and 80°.
drying, and characterized according to the procedures outlined The ultimate analysis was carried out using an EA3000
below. The biomass samples were dried according to the ASTM elemental analyzer (shimatzu Eurovector 3000). The procedure
E1756-08 standard until no weight variation was observed. involved combustion of the measured biomass sample under
However, it is important to note that during biomass storage, a controlled atmosphere, followed by analysis of the resulting
the moisture content may increase due to ambient humidity. gas products, to quantify carbon, hydrogen, nitrogen, sulfur,
Additionally, during the drying process, only the non-bound and oxygen contents in the samples. These ultimate analyses
water is evaporated, leaving some water molecules within the are conventionally presented on either a dry biomass basis or
structure of the biomass samples. a dry ash-free basis.
Thermal stability of biomass wastes was examined using
a Netzsch TGA/DSC thermogravimetric analyzer. The raw feed-
Physical and chemical characterization of feedstocks stocks were grounded and samples of 20 mg of each feedstock
The cellulose composition of biomass samples was assessed were placed in a crucible and heated from 25 °C to 900 °C at
following the procedure outlined by Kushner and Hoffer.25 a rate of 5 °C per minute under a constant ow of nitrogen,
Briey, the samples were immersed in a solution containing ensuring an inert atmosphere during pyrolysis.
nitric acid and ethanol in a 1 : 4 ratio for a duration of 4 hours. Proximate analysis provides information on the amount of
Subsequently, the samples were dryed in an oven set at 60 °C moisture, ash, volatile matter, and xed carbon present in
until a consistent weight was achieved. The quantication of a biomass sample. The thermogravimetric analysis method is
cellulose content (%cellulose = m2/m1 × 100) was calculated commonly used for proximate analysis to save analysis time.
with m1 the mass of the samples before treatment, and m2 aer The determination of moisture, volatile matter, and ash by
treatment. thermogravimetric analysis (TGA) is covered by the ASTM
The quantication of lignin content followed the ASTM D standard D7582-15, which involves recording the continuous
1106-96 standard methodology.26 Biomass samples underwent weight loss of the sample as it is heated. The TGA method for
treatment with an ethanol–toluene mixture at a ratio of 1 : 2 for proximate analysis is described in the ESI.†
a duration of 8 hours, with subsequent measurement of their The caloric values of the biomass waste samples were
mass. Subsequently, 1 gram of the biomass samples was stirred determined using the ultimate analysis based on the following
in a 15 mL solution of 72% sulfuric acid (H2SO4) for 2 hours. equation28 (HHV (MJ kg−1) = 0.2949%C + 0.8250%H), where
Following this, 560 mL of distilled water was introduced, and HHV represents the higher heating value, %C and %H repre-
the mixture was subjected to 4 hours of boiling. The residue sent the carbon and hydrogen content, respectively.
from this hydrolysis process was ltered via vacuum suction,
washed with 500 mL of heated water to eliminate all acid traces,
and subsequently dried in an oven maintained at 100 ± 2 °C for Photopyrolysis process setup and procedure
a period of 2 hours. The proportion of extracted lignin was Pulsed light setup description. The experimental congura-
determined (%lignin = m2/m1 × (100 − m3)), with m1 and m2 the tion of the pulsed light system used for biomass waste photo-
masses of biomass samples before and aer treatment, and m3 pyrolysis is illustrated in Fig. 2. The system consists of a simple
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stainless steel reactor sealed with a transparent window (boro- waste exhibited the lowest moisture content (44.19%), while
silicate glass or quartz), which allows the biomass samples to be Pennisetum alopecuroides displayed lower ash (4.76%) and xed
exposed to the high-power ash light from a Xenon lamp shown carbon (5.02%) percentages, making it a potentially an attrac-
in (Fig. S1†), in an inert atmosphere (argon). The reactor is tive material for thermochemical conversion processes, namely
placed on a heat-resistant table (Fig. S1,† inset 1) and then syngas and hydrogen rich-gas production. Pennisetum villosum
exposed to the ashing irradiation (Fig. S1,† inset 2) in showed a moderate moisture (54.89%) and volatile matter
controlled conditions of charging voltage, exposure time, pulse (31.54%) levels, offering a balanced composition for diverse
shape, etc., using a PulseForge 1300 photonic curing system biorenery applications. The investigated biomass wastes
(Novacentrix, USA). exhibited a varying ash content due to the presence of different
Three biomass wastes, i.e. Pennisetum alopecuroides, Penni- types of inorganic elements. Pennisetum alopecuroides and Pen-
setum villosum and onion waste ‘petiole and ower’, were nisetum villosum exhibit, otherwise, high mineral contents,
selected. They were dried at 105 °C for 24 h, in order to elimi- attributed to their elevated ash content.
nate any residual water and moisture, then ground and sieved. Ultimate analysis yielded the elemental compositions in
The resulting ne powder was subsequently utilized for further each of the studied samples, with Pennisetum villosum exhibit-
analysis. ing elevated nitrogen (2.32%) and oxygen (53.33%) contents
The photo-pyrolysis utilized ash-light irradiation in the compared to the other two substrates. Onion waste exhibited
form of 5 apparent ashes of 14.5 ms each, corresponding to a carbon content of 45.11%, making it a potential carbon-rich
a total exposure of 72.5 ms. The apparent ashes were separated feedstock for pyrolysis-based applications. Moreover, cellu-
by 3 seconds gaps providing a total ashing time of 12.2 s and lose, hemicellulose, and lignin contents were characterized to
an energy input of 13.1 J cm−2 each pulse. This energy-intensive understand the biomass structure and its implications for
light pulse was applied onto the loaded biomass, reducing the processing. Pennisetum alopecuroides exhibited the highest
biomass into biochar as illustrated in Fig. 2. A comprehensive cellulose content with a weight percentage of 42.53%, compared
description of this apparatus and the ashing procedure can be to Pennisetum villosum and onion waste with the corresponding
found in a previous work.16 percentages of 32.23% and 29.37%, respectively. The cellulose
The exhaust gases were analyzed using a PrismaPlus mass content of Pennisetum alopecuroides is close to that of Alfa,29
spectrometer (OMNISTAR GSD 320, Pfeifer), equipped with an which, as a consequence, makes it a promising candidate for
yttriated iridium lament. This step aimed to qualitatively cellulose-based materials. Pennisetum villosum, on the other
identify the gaseous products resulting from the photo-pyrolysis hand, demonstrated a remarkably high hemicellulose content
of the diverse natural biomass wastes. The system conguration (51.62%), making it a promising candidate for hemicellulose-
included a metallic tube outlet containing the generated gases, derived value-added products. Additionally, the lignin content
which was directly connected to the mass spectrometer's gas was relatively low in Pennisetum villosum (12.42%), potentially
inlet via a stainless-steel capillary. The mass spectrometer gas reducing the challenges associated with lignin valorization.
sampling line was maintained at a regulated temperature of Fixed carbon is dened as the biomass remaining aer the
200 °C over a length of 1 meter. release of volatile matter, excluding ash and moisture content.
This differs from the ultimate carbon content of the biomass
Results and discussion sample, as the carbon loss occurs in the form of hydrocarbons
during the release of volatile matter. The ultimate carbon
Primary characterization content is liberated in the form of both CO and xed carbon.
The chemical composition together with the ultimate and Both the volatile matter and the xed carbon contents
proximate analysis of the onion waste, the Pennisetum alope- signicantly inuence the thermochemical conversion process
curoides and the Pennisetum villosum without preliminary drying of these wastes. The interplay between these components is
are presented in Table 1. Proximate analysis revealed that for all highlighted by the ratio of volatile matter to xed carbon (VM/
three materials, signicant variations of moisture content, FC), revealing a noteworthy correlation with the hydrogen
volatile matter, ash, and xed carbon were detected. Onion content observed in the ultimate analysis.
To further characterize the biomass wastes, the high heating
value (HHV), representing the gross caloric value, was deter-
mined for all samples. The HHV was calculated based on the
ultimate analysis of the three-biomass wastes with the available
empirical formula and was found to range from 15.67–17.65 MJ
kg−1 in the studied biomass wastes.
The thermogravimetric (TG) curves shown in Fig. 3 indicates
that the weight loss of the biomass feedstocks ranges between
30 °C and 1000 °C for the 3 samples. TGA can be potentially
used to predict the pyrolysis behavior of each tested biomass
Fig. 2 (a) Overview of the biomass (feathertop plant) in the steel
waste. As deduced from the TG curves, the initial region of
reactor and (b) biochar obtained after photo-pyrolysis at 575 V-pulse weight loss, occurring between room temperature and 190 °C, is
and flashing time of 72.5 ms. mainly attributed to the elimination of moisture content and
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Table 1 Proximate analysis, ultimate analyses and composition of biomass wastes
Pennisetum Pennisetum
Analysis Onion waste alopecuroides villosum
Proximate analysis on raw matter Moisture (m%) 44.19 64.31 54.89

Volatile matter (VM) (m%) 39.16 25.91 31.54
Ash (m%) 5.67 4.76 6.59
Fixed carbon (FC) (m%) 10.98 5.02 6.98
VM/FC 3.84 5.16 4.52
HHV (MJ kg−1) 17.39 17.65 15.67
Ultimate analysis on dry matter N (%) 1.77 1.85 2.32
C (%) 45.11 42.43 38.85
H (%) 4.96 6.23 5.13

S (%) 0.98 1.64 0.34
Oa (%) 41.51 43.09 46.77
Composition Cellulose (%) 32.23 42.53 29.37
Hemicellulose (%) 37.33 34.86 51.62
Lignin (%) 26.75 15.85 12.42
a
The oxygen content was calculated on the ash free basis.
light volatile matter, particularly water-soluble hydroxyl and the three biomass wastes, respectively, which can be mainly
carboxyl groups present in the initial biomass waste.30 The attributed to the removal of moisture during the pyrolysis
major degradation occurs during the second stage, at temper- process. However, since the mass loss value is signicantly
atures between 190 °C and 440 °C, which can be further divided greater than the moisture content on a dry basis, the removal of
into two sub-stages. The rst sub-stage involves the breakage of some low molecular weight volatile components should also be
glycosidic bonds and thermal depolymerization of non- considered in the mass loss of this rst stage, in addition to the
cellulose groups, such as hemicellulose and pectin, while the moisture removal. Moreover, regarding the mass loss at this
second sub-stage is attributed to the decomposition of cellulose rst stage, it can be concluded that onion waste releases volatile
constituents.30,31 During the last stage, with temperatures matter much earlier than the other two biomass wastes.
ranging from 440 °C to 900 °C, the decomposition of residual The second stage was observed between 230 °C and 300 °C,
products shows a slow degradation prole due to the gradual where the respective mass loss rates of 17%, 25%, and 26% for
and constant decomposition of the complex lignin compound. the three biomass wastes were considerably higher compared to
The decomposition of lignin occurs at 540 °C. Beyond 900 °C, the rst stage. This is attributed to the initiation of the main
the remaining residue is considered as biochar, composed of devolatilization reactions, characterized by low thermal
carbon and mineral content. The amount of residual biochar stability, originating from the degradation of organic
depends on the characteristics of the feedstocks, namely xed compounds in the three biomass wastes. Based on previous
carbon and ash content. The residual biochar for onion waste, studies,32,33 hemicellulose is decomposed between 220 °C and
Pennisetum alopecuroides, and Pennisetum villosum was 27%, 330 °C, indicating that this second stage loss can be mainly
17% and 20% of the initial mass, respectively. These observed attributed to hemicellulose degradation.
values are in agreement with the proximate analysis of the three The third stage of the three biomass wastes occurred
wastes in terms of xed carbon and ash content (Table 1). between 300 and 425 °C, associated with a mass loss of 26%,
Fig. 3 illustrates the Derivative Thermogravimetric (DTG) 33%, and 27% for onion waste, Pennisetum alopecuroides, and
curves obtained for the biomass materials. As shown in Fig. 3, Pennisetum villosum, respectively. This mass loss was higher
all materials exhibited three main peaks, corresponding to the than in the previous stages, indicating the continuation of
decomposition of hemicellulose, cellulose, and lignin at devolatilization reactions. Therefore, the mass loss of the third
distinct temperature ranges. Up to a temperature of 250 °C, the stage can be attributed predominantly to the thermal degrada-
mass loss recorded was approximately 23%, 15%, and 13% for tion of a component with higher thermal stability than
Fig. 3 TGA and DTG curves of (a) Pennisetum villosum (b) Pennisetum alopecuroides and (c) Onion waste.
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hemicellulose. It is reported that cellulose is characterized by materials.37,38 Overall, the observed FTIR bands and functional
high thermal stability with a degradation that occurs mainly in groups align with the characteristics of lignocellulosic mate-
the range of 300 °C to 410 °C.33,34 Therefore, this third stage can rials, further conrming the nature of the three biomass waste
be mainly attributed to cellulose degradation and partial lignin samples. These results are in accordance with reported values
degradation. on Table 1.
The fourth stage occurs between the temperatures of 425 °C Fig. 5 shows the XRD patterns of the analyzed biomass
and 900 °C and is characterized by a mass loss of 9.4%, 17%, materials. Cellulose, a structurally pivotal component, is
and 15% for the three biomass samples, respectively. The mass inherently characterized by a coexistence of amorphous and
loss of this fourth stage can be attributed mainly to the degra- crystalline domains.39 In contrast, lignin and hemicellulose are
dation of the most thermally stable component in the structure predominantly amorphous in nature.37,38 The overarching
of the three biomass wastes, which is lignin. Lignin is reported lignocellulosic matrix, however, exhibits a multifaceted
to undergo thermal degradation within a wide temperature arrangement wherein the amorphous fraction may be
range spread between 150 °C and 1000 °C.33,34 predominant. The signicant presence of amorphous regions
TGA-DTG analysis is a crucial and potentially informative contributes to a pronounced background signal that obscures
characterization technique to evaluate the behavior of different the sharp signals arising from crystalline regions.36,37 The pre-
biomass wastes during the pyrolysis process. Therefore, from sented XRD ndings distinctly illustrate this phenomenon, with
this analysis, it can be concluded that at approximately 500 °C, a broad peak dominating around 2q at 20.84° for all samples.
the majority of volatile compounds are generated, with amounts The distinctiveness of this broad peak, suggests a semi-
of 66%, 63%, and 65%, excluding moisture, for the three crystalline nature of the biomass samples structure.39 This can
biomass wastes, respectively. Hence, for liquid (oil) production, be attributed to intricate interactions between the hydroxyl (–
a pyrolysis temperature of 500 °C should be sufficient. OH) groups of cellulose and the carbonyl (C]O) groups of
The obtained FTIR spectra for the three-biomass waste hemicellulose and lignin.36 Furthermore, differentiation among
samples, are presented in Fig. 4, where characteristic absorp- the XRD proles of the biomass samples is rooted in their
tion bands of the various chemical compounds are shown. A polycrystalline nature, a consequence of varying cellulose
prominent peak at 3343 cm−1 was observed in all three spectra, content within each sample.38
indicating the stretching vibration of O–H bonds in cellulose.35
Another strong peak at 1044 cm−1 is attributed to C–O Photopyrolysis
stretching vibrations in both hemicelluloses and cellulose.
Each biomass waste was subjected to photo-pyrolysis with the
Furthermore, the spectra displayed bands in the region of 1650–
conditions described above for a dry matter quantity of 10 mg
1440 cm−1, which are characteristic of C]C bonds. These
per test.
bands were predominantly associated with aromatic
As a result of photo-pyrolysis, the 10 mg of onion waste
compounds found in lignin, a major component of lignocellu-
(ower and petiole) resulted in 2 mg of biochar, while the
losic materials.30,36 Additionally, a consistent peak at 1645 cm−1
feathertop plant (Pennisetum alopecuroides) and the feathertop
was present in all samples, suggesting the presence of both
plant (Pennisetum Villusom) yielded 1.9 mg and 2.1 mg,
water molecules and C]O bonds of hemicelluloses. Moreover,
respectively.
a noteworthy peak at 1438 cm−1 was observed, indicating the
Higher temperatures are known to enhance the decompo-
presence of C–H bending vibrations, primarily attributed to
sition of solid waste, promoting secondary reactions that
cellulose, another integral component of lignocellulosic
increase the yield of syngas, primarily composed of CH4, H2,
CO, and CO2. Consequently, the mass yield of biochar is directly
inuenced by the intensity and duration of the light ashes. A
Fig. 4 FTIR spectrum of the biomass wastes. Fig. 5 X-ray diffractogram of the different biomass wastes.
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direct correlation between the xed carbon content of the decomposition of the three types of biomass during the photo-
biomass and the biochar yield40 was established, as well as the pyrolysis process varies, dependent on the processing condi-
volatile matter content and the bio-oil yield in the photo- tions, mainly temperature. Several studies have shown that
pyrolysis process. The differences in the mass of biochar pyrolysis temperature is an important parameter that strongly
generated between the three photopyrolyzed biomass samples inuences product distribution. Moreover, the increase of the
are relatively minor, with approximately 20% of the initial mass process temperature will directly lead to an increase in the
remaining aer the photo-pyrolysis process. thermochemical conversion of the biomass waste resulting in
When considering the TGA-DTG results, the remaining mass the release of higher quantities of compounds, and thus a lower
fraction of onion waste is the highest, followed by Pennisetum remaining fraction of biochar. This decrease can be attributed
villusom and then Pennisetum alopecuroides. This trend is to secondary cracking reactions in the bio-oil, which favors
consistent with the proximate analysis of the three samples in a higher formation of lower molecular weight compounds and
terms of xed carbon and ash content, with onion waste having gas products. Moreover, high temperature may also led to char
the highest content, followed by Pennisetum villusom and Pen- residue decomposition. Consequently, the higher biochar yield
nisetum alopecuroides. These results suggest that the at lower pyrolysis temperatures indicates incomplete or partial
biomass decomposition, thus justifying the slight differences
observed in the biochar yield for the three-biomass wastes. It is
important to note that the biochar generated in this process is
in a liquid–solid state, commonly referred to as ‘oily’. Therefore,
further treatment is necessary to convert this biochar into
a suitable form for applications such as hydrogen storage or
CO2 capture.
Cellulose-rich biomass is better suited for liquid production,
whereas biomass rich in hemicellulose is more suitable for
syngas production.41 Biomass with high lignin content, on the
other hand, serves as an excellent feedstock for biochar
production.42 However, it is worth noting that many simulations
and studies have demonstrated that relying on a single biomass
pyrolysis product may not yield favorable economic benets.4
Therefore, enhancing the value of by-products, such as biochar
Fig. 7 Comparison of the ionic currents of (a) m/z 2 (H2), (b) 15 (CH4),
Fig. 6Ionic currents for m/z 2 (H2), 15 (CH4), 26 (C2H4), 28 (CO), 29 (c) 26 (C2H4), (d) 28 (CO), (e) 29 (CH3CHO) and (f) 44 (CO2) obtained
(CH3CHO) and 44 (CO2) obtained during the flash light irradiation at during the photo-pyrolysis of Pennisetum alopecuroides, Pennisetum
575 V-pulse and 72.5 ms from different biomass: (a) Pennisetum alo- villosum and onion waste by flash light irradiation at 575 V-pulse and
pecuroides, (b) Pennisetum villosum and (c) onion waste. 72.5 ms.
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Paper RSC Advances
Table 2 Number of moles and dry mass composition of the three biomass samples based on 100 g wet samples
Onion waste Pennisetum alopecuroides Pennisetum villosum
Number of moles Dry mass Number of moles Dry mass Number of moles
Dry mass (g) (mole) (g) (mole) (g) (mole)
Fixed carbon 6.12 0.51 1.8 0.15 3.15 0.26

C 45.11 2.09 42.43 1.26 38.85 1.46
H 4.96 2.77 6.23 2.22 5.13 2.31
Oashfree 41.51 1.45 43.09 0.96 46.77 1.32
N 1.77 0.07 1.85 0.04 2.32 0.07
and syngas, becomes a pivotal strategy to mitigate the impact of Conclusion

various biomass feedstocks on the nal products.
The gas produced during photo-pyrolysis was analyzed using This study is a contribution to the exploration of biomass
online mass spectroscopy (MS), and the results are presented in feedstock in Morocco to produce high-value products, speci-
Fig. 6 and 7 for the three biomass wastes. Various gas products cally biochar and syngas or hydrogen-rich gas. The innovative
are generated during the photopyrolysis process, with a high approach was to employ photo-pyrolysis as a screening tool for
ionic current attributed to hydrogen and carbon monoxide. The biomass processing, which enhance the efficiency of this
ionic current of acetaldehyde is the lowest, while ethylene, investigation. This rapid pyrolysis process, coupled with
methane, and carbon dioxide fall in the middle range in terms Mass Spectrometry (MS), not only rivals the classical ultimate
of ionic current. The higher signal intensities for H2 and CO, analysis but also yields more comprehensive results compared
and the lower intensities for CO2, CH4, C2H4, and CH3CHO to established pyrolysis techniques such as TGA-MS and
collected under the photopyrolysis conditions for the three FTIR-MS.
biomass wastes, suggest that the released gas is a hydrogen-rich The analysis of the gas composition from three distinct
gas. The use of biomass wastes in their wet conditions may biomass wastes in this study provides crucial insights into their
thermodynamically lead to more hydrogen formation, following thermochemical characteristics. The application of photo-
the water gas shi reaction (CO + H2O # CO2 + H2).2 Several pyrolysis, with its rapid and informative capabilities, not only
reactions take place during the biomass ash photopyrolysis enhances our understanding of these characteristics but also
a series of these reactions are given in the ESI.† creates paths for optimizing the conversion of biomass into
To further understand biomass decomposition during the valuable energy products, thereby contributing to carbon miti-
photopyrolysis process, Table 2 provides a detailed breakdown gation efforts.
of the composition of the three biomass wastes in terms of dry The results obtained from this study play a dual role,
mass (dm) and molar number (moles) based on 100 g of each expanding our knowledge of the potential of Moroccan biomass
wet sample. Analyzing the compatibility of atoms and mass resources for carbon and syngas or hydrogen-rich gas produc-
helps deepen our understanding of the conversion process to tion, while also advancing the characterization process of waste
produce syngas or hydrogen-rich gas. materials. This enhanced characterization is pivotal in revealing
If we assume that the oxygen in the 100 g of samples, which the potential of these wastes in the renewable energy sector.
amounts to 1.45, 0.96, and 1.32 moles of oxygen atoms present
in onion waste, Pennisetum alopecuroides, and Pennisetum vil-
lusom, respectively, is totally used to form CO (see Fig. 6 and 7), Author contributions
the remaining carbon would be 0.64, 0.30, and 0.14 moles for
the three wastes, respectively, which is higher than the xed A. Mellalou: conceptualization, formal analysis, investigation,
carbon of the three biomass samples, suggesting that other methodology, validation, writing – original dra. Wanderson O.
carbon containing volatile products have been formed. Silva: conceptualization, formal analysis, investigation, meth-
In addition, the expected maximum number of moles of odology, writing – review & editing. Mathieu Soutrenon: formal
analysis, investigation, writing – review & editing. Hubert H.
hydrogen that are used to form H2 would be 2.77, 2.22, and 2.31
Girault: formal analysis, investigation, supervision, writing –
moles for the three biomass samples, respectively. Assuming that
the VM is mainly composed of H2 and CO, the resulting quantities review & editing. A. Outzourhit: formal analysis, supervision,
of CO would be 1.22, 0.85, and 0.94 moles for the three samples, writing – review & editing. J. Alami: formal analysis, funding
respectively. Comparing the generated CO amounts to the molar acquisition, writing – review & editing. F. Ghamouss: formal
amount of O in each sample reveals a difference of 0.23, 0.11, and analysis, funding acquisition, investigation, validation, super-
0.38 moles for the three biomass samples, respectively. Therefore, vision, writing – review & editing.
based on this simple comparison, we conclude that other
oxygenated molecules are produced such as CO2 and CH3CHO, in
addition to perhaps NOx molecules, which is in qualitative
Conflicts of interest
agreement with observed results from the MS analysis. There are no conicts to declare.
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RSC Advances Paper
20 H. W. Cui, J. T. Jiu, T. Sugahara, S. Nagao, K. Suganuma,

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Biomass screening for syngas production by ﬂash

Abderrahman Mellalou, a Wanderson O. Silva, b Mathieu Soutrenon, b

Hubert H. Girault, c Abdelkader Outzourhit,d Jones Alamia

emission-free utilization is promising in the reduction of air

Paper RSC Advances

the Poaceae family, as depicted in Fig. 1a. Indigenous to