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Multifaceted analysis of products from the intermediate co-pyrolysis of

biomass with Tetra Pak waste

Article in International Journal of Hydrogen Energy · July 2021

DOI: 10.1016/j.ijhydene.2021.06.202

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journal homepage: www.elsevier.com/locate/he

Multifaceted analysis of products from the

intermediate co-pyrolysis of biomass with Tetra
Pak waste

Wojciech Jerzak*, Artur Bieniek, Aneta Magdziarz

AGH University of Science and Technology, 30 Mickiewicza Av., 30-059, Krakow, Poland

highlights

Gas, tar, wax, char, and aqueous phases from biomasseTetra Pak co-pyrolysis were studied.

CO2 and CxHy concentrations exhibited two local maxima over the pyrolysis time.

Aromatic compounds were detected in tars and waxes.

Addition of Tetra Pak to biomass enhanced hydrogen production during co-pyrolysis.

The aqueous phase contained between 12% and 22% C.

article info abstract

Article history: This study investigates the co-pyrolysis of two types of biomass (pine bark and wheat
Received 19 February 2021 straw) with Tetra Pak waste (TPW). The experiments were performed using a fixed-bed
Received in revised form reactor equipped with an innovative system, where a sample was rapidly heated to
27 May 2021 600  C before being rapidly cooled. The multifaceted analysis included the determination of
Accepted 24 June 2021 the i) physical and chemical properties of the feedstocks and chars, ii) aqueous phase, tars,
Available online 14 July 2021 and waxes, iii) char ignition and burnout temperature, iv) chemical composition of gas, and
v) distribution of carbon and hydrogen in the obtained products. The results showed that
Keywords: the addition of TPW to the both types of biomass significantly reduced the char mass and
Co-pyrolysis aqueous phase, decreased the carbon, hydrogen, and nitrogen contents of the char, and
Biomass increased the wax and tar yields retained in the water cooler. Different organic compounds
Tetra pak such as alkenes, aromatic hydrocarbons, and acids were found in tars and waxes. The
Fixed bed reactor chemical composition of the released gases was detected in situ (by a flue-gas analyser)
Tar and wax and ex-situ (using gas chromatography). Changes in the concentrations of H2, CH4, CO, CO2,
and C2eC4 were observed. The addition of Tetra Pak to the two types of biomass had an
evident and positive effect on the hydrogen content of the pyrolysis gas.
© 2021 The Authors. Published by Elsevier Ltd on behalf of Hydrogen Energy Publications
LLC. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding author.
E-mail address: wjerzak@agh.edu.pl (W. Jerzak).
https://doi.org/10.1016/j.ijhydene.2021.06.202
0360-3199/© 2021 The Authors. Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4
Introduction
Agricultural and forest residues are widely available and
provide potential raw materials for sustainable energy pro-
duction in the future [1,2]. Raw biomass, paper waste, and
sewage sludge contain organic matter and can be converted
into valuable products [3,4]. Other important materials that
can be used for energy production include municipal solid
waste (MSW) [5]. Every year, a huge amount of waste is pro-
duced by human activities, which represents a major problem
for proper waste management. Accordingly, Tetra Pak is a
component of MSW that is worth considering for thermal
utilisation.
The reduction of greenhouse gas emissions is the driving
force behind research into energy production based on the
pyrolysis of biomass and waste [6]. Pyrolysis is one of the most
promising and effective techniques for producing biofuels
from organic feedstocks. During pyrolysis, the thermal
degradation of chemical compounds in biomass (or another
solid feedstock) occurs in the absence of an oxygen atmo-
sphere. The most important parameters influencing pyrolysis
are the vapour residence time and heating rate. Generally,
pyrolysis occurs in the temperature range of 300e1000  C
(Table 1). The product yield depends on various parameters of
the pyrolysis process. In particular, the vapour residence time
allows pyrolysis to be categorised into different subclasses:
slow, intermediate, fast, and flash. Table 1 shows the oper-
ating conditions of these different subclasses.
Char, liquid, and gas are always produced during pyrolysis.
Slow pyrolysis occurs under low reaction temperatures and
over long vapour residence times, which promote charcoal
production [7,8]. In turn, moderate temperatures and short
vapour residence times favour the production of the liquid
phase during fast pyrolysis [9,10]. A higher pyrolysis temper-
ature favours the decomposition reactions of the raw mate-
rial, thus increasing the yields of the liquid and gaseous
fractions. The organic liquid yield of the fast pyrolysis process
is more than double that of the intermediate pyrolysis process
when using a biomass with a low ash content [11]. Research
on the intermediate pyrolysis process began relatively
recently (2011), thanks to the world's first pilot-scale reactor
developed by Hornung et al. [12]. The yields of the interme-
diate pyrolysis products have been estimated as follows: 35
%e50% liquid, ~30% char, and 20 %e35% gas [13,14]. Increasing
the heating rate improves the liquid and gas yields [14].
Moreover, positive correlations between the pyrolysis tem-
perature and the gas and liquid yields have been observed in
several studies [15,16]. The liquid phase produced by the in-
termediate pyrolysis of biomass is appealing because of its
relatively low tar content. The intermediate pyrolysis pro-
duces a two-phase liquid: aqueous phase with low calorific
value and pyrolysis oil [17]. The pyrolysis oil contained in the
two-phase liquid can be easily separated from aqueous phase
under gravity. As suggested by Torri and Fabbri [18], methane
can be produced from an aqueous phase in anaerobic
11681
digestion using the char additive. Furthermore, the interme-
diate pyrolysis reactor can produce a high-quality fuel gas
containing more than 50% combustible components (CO, CxHy
and H2) [13].
The co-pyrolysis of biomass and waste is an attractive
method for increasing the hydrogen (H) content of the resul-
tant gas and improving the quality of bio-oils [19,20]. Many
Tetra Pak pyrolysis experiments have been reported in recent
publications [21e24]. Not only the pyrolysis temperature, but
also the storage time of Tetra Pak and the fineness of the
feedstock have major influences on the product yields [21].
The increase in the size of the Tetra Pak particles inhibits the
heat flow inside the material and hinders the degassing pro-
cess. Haydary et al. [22] investigated catalysed Tetra Pak py-
rolysis for reducing the tar content. The use of dolomite as a
catalyst resulted in the best reduction of tar at 850  C. During
the Tetra Pak pyrolysis process, wax is always formed in
addition to char, liquid, tar, gas, and aluminium (Al) [23].
Depending on the process temperature, the wax content of
the products may exceed 20% by mass. It has also been re-
ported that carbon monoxide (CO) is the dominant component
of pyrolysis gas, which arises primarily from the degradation
of cardboard. The formation of aldehydes, ketones, carboxylic
acids, and levoglucosan is attributed to cellulose decomposi-
tion, while the thermal cracking of polyethylene is responsible
for the presence of aliphatic hydrocarbons [24].
The co-pyrolysis of various types of biomass and other
feedstocks has a positive effect on product quality and process
efficiency, which has been confirmed by numerous studies
[20,25,26]. An increase in the pine bark (PB) percentage content
in a mixture with waste tyres was found to improve the
quality of the gas yield [25]. Additionally, the peak flow rates of
H2 and CO in the total gas increased. Farooq et al. [20] reported
that adding waste tyres during wheat straw (WS) pyrolysis
caused an increase in the aqueous phase yield. The oxygen
content and viscosity of the oil decreased in comparison to
that of WS pyrolysis without tyre addition. During the co-
pyrolysis process, the thermal degradation of biomass and
synthetic polymers (polyethylene, polypropylene, and poly-
styrene) overlap and may lead to interactions between the
vapour products [26].
The purpose of this study is to experimentally investigate
the intermediate co-pyrolysis of two biomass materials (PB
and WS) with Tetra Pak packaging. The intermediate pyrolysis
method brings significant benefits because all pyrolysis
products (char, liquid phase, and gas) are characterized by
high energetic quality comparing to other pyrolysis types. It
should be clearly emphasised that intermediate pyrolysis is a
relatively new thermal technology, and to the best of our
knowledge, relatively few studies have been published in this
area. The present study aims to determine how adding Tetra
Pak to PB and WS affects the i) product yields, ii) carbon (C) and
hydrogen (H) contents of co-pyrolysis products, iii) distribu-
tion of C and H in co-pyrolysis products, iv) ignition and
burnout temperature of chars, v) in situ and ex situ analyses of
gas components, and vi) identification of compounds in tars
11682 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4

Table 1 e Main operating parameters for pyrolysis processes [7e10].

Operating parameter Pyrolysis
Slow Intermediate Fast Flash

Temperature ( C) 300e700 450e700 450e1000 800e1000
Heating rate ( C/s) 0.1e1 1e70 10e200 >1000
Vapour residence time (s) >10 10e30 0.5e20 <0.5

and waxes. The results will provide knowledge about the ef- The results of the ultimate, proximate, and component
fect of the co-pyrolysis of biomass and Tetra Pak, and support analyses are presented in Table 2, which shows that the
the development of more environmentally friendly co- constituents of the PB used in this study were ranked as:
pyrolysis processes. lignin > cellulose > hemicellulose. A dominant lignin content
in PB has been confirmed in previous studies [30,31]. In
contrast, the constituents of the WS were ranked as:
Material and methods hemicellulose > cellulose > lignin. The obtained contents of
lignin, hemicellulose, and cellulose agreed with those deter-
Feedstocks mined by Ding et al. [32] and Demirbas [33].

Tetra Pak waste (TPW), PB, and WS were used as feedstocks for Experimental method
the experiments. The PB used in this study came from a
sawmill specialising in supplying wood for windows, stairs, Experimental stand with a fixed-bed reactor
doors, and kitchen furniture. Considering the need to reduce The main goal of this study is to investigate the intermediate
straw surpluses in Poland, which is estimated to be 11  106 t/a co-pyrolysis process in a horizontal fixed-bed reactor with an
[27], WS was selected for the pyrolysis process. As a repre- electric heater. The experimental setup is illustrated in Fig. 1.
sentative of MSW, Tetra Pak consists of 70% paperboard, 25% The setup consisted of three zones: cooling I, heating, and
low-density polyethylene (LDPE), and 5% Al foil [28]. The cooling II. In the first cooling zone, an inert gas (N2) was sup-
sources of TPW include packaging for juice, milk, and wine, as plied, and after pyrolysis, the solid residue was cooled. The
well as six-layer packaging. sample was then placed in the heating zone and the pyrolysis
Biomass mixtures of PBeTPW and WSeTPW were pre- process was conducted. Tar vapour flowed along the heated
pared at 25%, 50%, and 75% by mass. The following conven- horizontal tube of the reactor to approach the final stage. The
tions were adopted for labelling and referring to samples: temperature profiles from the centre to the end of the reactor
100% mass feedstocks are referred to as PB, WS, and TPW, (length: 190 mm; diameter: 15 mm) were monitored using
while the mass mixtures are referred to as 25PBe75TPW (25% three K-type thermocouples, as shown in Fig. 2. Moreover, a
mass PB and 75% mass TPW), 50PBe50TPW, 75PBe25TPW, thermocouple was inserted horizontally into the centre of the
25WSe75TPW, 50WSe50TPW, and 75WSe25TPW.
Before the main investigation, all the materials went
through pre-treatment processes. The raw biomasses were
Table 2 e Results of the analyses of the PB, WS, and TPW
then dried under ambient conditions before being ground and samples at the air-dry state.
sieved. Finely-ground PB and WS particles (range of
Sample PB WS TPW
0.2e0.3 mm) were selected for further investigation. Tetra Pak
waste was cut into small square or rectangular pieces Proximate analysis (mass %)
Moisture (M) 10.10 7.53 3.28
(maximum dimensions of 1 mm  2 mm). The Al foil consti-
Volatile Matter (VM) 61.05 70.59 78.73
tuted 6.23% (by mass) of the sample. An additional investiga-
Ash (A) 0.89 6.06 12.27
tion of the Al foil using scanning electron microscopy with Fixed Carbon (aFC) 27.97 15.82 5.72
energy dispersive X-ray spectrometry (SEMeEDS) did not Ultimate analysis (mass %)
reveal its oxidation after pyrolysis. It is well known that only C 48.50 43.70 49.43
non-oxidised Al foil is recyclable. H 5.90 6.11 7.46
Ultimate, proximate, and component analyses of the three N 0.17 0.52 0
S 0.029 0.098 0.055
feedstocks (PB, WS, and TPW) were performed. In the ulti- b
O 45.53 49.57 43.06
mate analysis, the contents of C, H, nitrogen (N), and sulfur (S) Component analysis (mass %)
elements were determined using a Truspec CHNS 628 Leco Cellulose 22.54 25.14 71.02c
analyser. In the proximate analysis, the moisture, volatile Hemicellulose 5.68 32.13 13.07c
matter, and ash contents were determined in accordance Lignin 49.20 12.64 12.41c
with the following standards: EN ISO 18134e2:2017 (for Extractives 22.58 30.09 3.50c
moisture), EN ISO 18122:2015 (for volatile matter), and EN ISO Where.
a
18122:2015 (for ash). In the component analysis, the cellulose, FC ¼ 100 e M  VM e A.
b
hemicellulose, and lignin contents of the samples were O by difference, ash free, Al foil free.
c
LDPE, and Al foil free.
determined using the Van Soest method [29].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4
Fig. 1 e Experimental setup for the intermediate co-pyrolysis process.
Fig. 2 e Temperature of the sample and reactor at the
designated points during the experiment.
sample. Prior to inserting the sample into the heating zone,
the oven temperature was set to 620  C (blue line in Fig. 2).
When the sample was introduced into the heating zone, its
temperature increased rapidly (red line from 0 s to 300 s in
Fig. 2), and the furnace temperature was lowered. The tem-
perature was recorded every 0.1 s of pyrolysis by fully auto-
matic measurements. The flow rate of high-purity N2
(99.9999%) was 100 mL/min, which was constant during the
experiment. The volume flow rate was measured using a
rotameter. The vapour residence time in the heating zone was
20.1 s, which corresponds to intermediate pyrolysis according
to Table 1.
The third area (cooling zone II, on the left side of Fig. 1)
provided two-stage gas cooling. Firstly, the gas was cooled to
18  C (in water cooler), and next to approximately 4  C (in an ice
container), thus allowing heavy hydrocarbons to condense.
11683
The uniqueness of this study is the insertion of a cold
sample into a preheated reactor. The proposed method
allowed a quick heat supply to the sample from ambient
temperature to the pyrolysis temperature. For these cases, 1 g
samples were inserted into the heating zone. Each sample was
kept in a reactor for 300 s. The sample was able to attain 600  C
at this time. The pyrolysis gas was cooled in two stages. In the
first stage, the temperature of the vapours was decreased by a
water heat exchanger. Condensed heavy hydrocarbons (i.e.,
tars and waxes) were collected for further analysis. In the
second stage, hydrocarbon vapours flowed into an ice tank.
This allowed the collection of liquefied hydrocarbons, which
are characterized by a lower condensation temperature. The
concentrations of the gas components were measured using a
Land Lancom 4 analyser. Before the gas components were
analysed, they were diluted by adding 1600 mL/min of pure N2.
The gas dilution aimed to prevent the analyser from
exceeding the measuring ranges of CO, CO2, and CxHy, and to
ensure a rapid response of the device to concentration
changes over time. At high concentrations, the saturated CO
electrochemical sensor exhibited a relatively long response
time. Solid residues were rapidly removed from the heating
zone to cooling zone I after pyrolysis.
Thermogravimetric analysis
The weight loss of each feedstock and char was determined
under an air atmosphere using a thermal analyser (Mettler
Toledo TGA/SDTA 851). Air was delivered at a constant flow
rate of 40 mL/min. In each experiment, approximately 6 mg of
sample was placed in a corundum crucible, and the heating
rate was fixed at 10  C/min from the ambient temperature
(25  C) to 700  C (only the Tetra Pak char was heated up to
800  C). The weight loss, time, and temperature were recorded
simultaneously and were used to produce the combustion
profile. The thermal parameters, including the ignition tem-
perature (Ti) and burnout temperature (Tb), were determined
using the thermogravimetry (TG)ederivative TG (DTG)
graphical method [34]. The temperatures were defined as
11684 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4

follows: Ti is the minimum temperature at which fuel ignites

spontaneously in an environment without an external source
of ignition, and Tb is the temperature at which the fuel con-
version reaches 99%.

Char, aqueous phase, tar and wax, and gas analysis

The resultant char, aqueous phase, condensed gases, tar, and

wax were weighed. Each time (for the implemented variant), the
measurement results were averaged based on tests carried out
for 20 samples. The ultimate analysis (C, H, and N) were deter-
mined using the Truspec CHNS 628 Leco analyser. The liquid
phase (aqueous phase þ tarry compounds and wax) was
collected in the first condenser (Fig. 1). Rapid cooling of inter-
mediate pyrolysis products led to tar and wax retention on the
inner surface of the water cooler pipe. After the end of pyrolysis
process (for each variant), with the N flow maintained, the water
cooler was fed warm water at a temperature of ~50  C, and tar
and wax were removed by melting. The melting point of paraffin
waxes, which mostly contain unbranched alkanes, is within the
range of 50e70  C [35]. Tar and wax exhibited a plastic consis-
tency at ambient temperatures. In the second condenser (Fig. 1),
only condensed gas was collected at temperatures of
4  C  T < 18  C. The composition of the gas was measured online
using the Lancom 4 analyser. The following sensors were
installed in this gas measuring device: electrochemical (for CO),
infrared (for carbon dioxide (CO2)), and pelistor (for CxHy). To
ensure that the concentrations of the measured gas components
did not exceed the measurement range of the device, we used
the gas leaving the pyrolysis reactor after it was diluted with N2,
which also improved the analyser response time to changes in
the gas concentrations. In addition, the hydrocarbon composi-
tion and H2 content of the gas were analysed using an Agilent
Technology 7890A gas chromatograph (GC). The analysis of the
gases collected in the Tedlar bags represents the average
composition from a process lasting 300 s. In turn, the identifi-
cation of tar and wax components was performed using
GCemass spectrometry (MS) (Agilent GC 7890 B equipped with
an MS 5977A mass spectrometer and a flame ioniser detector).
The tar and wax analyses were carried out on the basis of the
evaporation of compounds from samples heated at a rate of 3  C/
min from 40  C to 250  C (the samples were kept at the initial and
final temperatures for 7 min and 10 min, respectively).

Results and discussion

At the beginning, it is worth to emphasize that both yield and
elemental char analysis are closely related to the sample
heating and cooling system. As shown earlier in Fig. 2, the
sample was rapidly heated and after 90 s its temperature was
500  C. Then the heating rate of sample was adjusted to obtain
600  C after 300 s. The first cooling zone played a very
important role in the results presented later in this paper.
Char was quickly cooled, after 60 s, temperature was approx.
300  C, and it allowed to eliminate the release of volatile
matter after the time designated for the co-pyrolysis process.
The second cooling zone also played an important role. Rapid
cooling of the pyrolysis gas to 18  C in a water cooler had
resulted easy condensation of tars and wax, consequently, the
Fig. 3 e Char: a) yield, and ultimate analysis from the co-
pyrolysis of b) PBeTPW and c) WSeTPW.
aqueous phase was collected in the first condenser. It
confirmed that applied technical solution is adequate for
efficient collection of products.
Char
Yield and ultimate analysis
Fig. 3a shows how the addition of TPW to the two biomasses
affected the char yield (without Al foil). According to Table 2,
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4 11685

the PB used in this study contained 49.2% lignin, while the WS
only contained 12.6% lignin. The lignin content of a given
biomass is mainly responsible for char formation [32,36], and
resulted in a higher char content from PB pyrolysis than from
WS pyrolysis. The mass of the TPW char constituted only
19.8% of the initial mass of the TPW feedstock. Similar results
have been reported in previous studies [21,23]. The higher the
TPW content in the co-pyrolysed mixtures, the lower the char
mass obtained. In addition, the PB feedstock contains inor-
ganic species such as K, Ca, Si, and Al [37], the presence of
which would have strongly catalysed the decomposition of PB
and promoted char formation.
The ultimate analysis results of the studied chars are
shown in Fig. 3b and c. The PB char contained a C content of
81.0%, whereas the WS char contained only 64.2%, which were
both comparable to those reported in other studies [25,38]. As
shown in Fig. 3b and c, the PB and WS chars were of the
highest class according to the International Biochar Initiative
classification (i.e., class 1 for a C content of 60%) [39].
From an energy point of view, the PBeTPW chars were
more attractive than the WSeTPW chars. The percentage
change of carbon (DCÞ is calculated from the equation:
Cchar  Cfeedstock
DC ¼ ,100 % (1)
Cfeedstock
The DC increased in the chars compared to their respective
feedstocks (Table 2), whereby the PB, WS, and TPW chars had
the DC values of 67%, 47%, and 16%, respectively. As expected,

Fig. 4 e TG and DTG curves for feedstocks and chars from a) PB, b) WS, and c) TPW, and chars from the co-pyrolysis of PB and
WS biomasses with d) 25TPW, e) 50TPW, and f) 75TPW.
11686 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4
Fig. 5 e Ignition and burnout temperatures for feedstocks and chars from the co-pyrolysis of a) PBeTPW, and b) WSeTPW.
the H content of the PB, WS, and TPW chars reduced in com-
parison to their feedstocks because H evaporated and trans-
ferred to the tar, wax, and gas phases. The TPW sample lost
the most H (67%) compared to the initial value (before pyrol-
ysis), even though the TPW was the least fragmented among
the studied feedstocks.
Nitrogen was only detected in the TPW analysis.
Comparing the N contents of the raw biomass samples with
those remaining in the chars (char-N) revealed a clear in-
crease from 0.17% to 0.4% (for PB) and from 0.52% to 1.42%
(for WS).
Characteristic combustion temperatures from TGeDTG
The TG and DTG curves of the investigated feedstocks and
chars under air conditions are presented in Fig. 4aef. Feed-
stock combustion occurred in three stages (Fig. 4aec). An
initial mass loss occurred at ~200  C, which was mainly due to
moisture evaporation. The second stage reflected the release
of volatile matter associated with the depolymerisation of
hemicellulose, cellulose, and lignin. The DTG results showed
that the first peak of combustion was attributed to hemicel-
lulose decomposition (150e310  C), cellulose decomposition,
and lignin degradation (310e400  C) [40]. The second peak of
the DTG curves corresponded to lignin decomposition
(>450  C) [40], and was most visible for the PB sample (Fig. 4a),
thus reflecting its higher lignin content among the feedstocks
(Table 2).
The last stage began at the burnout temperature (Tb). In
addition, in the case of TPW, two small peaks were observed at
407  C and 644  C. The first peak may reflect LDPE degradation,
while the second peak reflects the thermal decomposition of
the remaining paper.
On the Al foil [41]. The char combustion profiles were quite
different to those of the feedstock profiles. The DTG curves of
the PB, WS, and TPW chars (Fig. 4aec) showed single peaks at
ca. 464  C, 390  C, and 437  C, respectively. In conclusion, our
results confirmed the degradation of hemicellulose and the
release of lower volatile matter during the pyrolysis of the
studied biomass feedstocks.
Fig. 5a and b displays the Ti and Tb temperatures deter-
mined by the graphical method (Section Thermogravimetric
analysis). The lowest Ti and Tb values (258  C and 470  C,
respectively) were obtained for the WS feedstock. The higher
volatile matter content of biomass indicates a better fuel
reactivity and lower Ti, as reported in the literature [42].
In turn, a lower Tb indicates better combustion for a shorter
residence time in the furnace. The PB, WS, and TPW chars had
higher Ti and Tb values than the corresponding feedstocks.
The difference between the Ti values (DTi) of the PB and TPW
chars (DTi(PB - TPW)) was only 7  C, whereas DTi(WS - TPW) was
62  C. In contrast, DTb(PB - TPW) was 171  C, while DTb(WS - TPW)
was 109  C. The Tb values of the PBeTPW and WSeTPW chars
increased almost linearly.
Aqueous phase: yield and ultimate analysis
The liquid product consisted of an organic aqueous phase and
a sticky phase (tars and waxes). A gravimetric settler was used
to separate the aqueous phases. The source of water in the co-
pyrolysis products was the moisture of the feedstock and the
reactions of H and O released from the PB, WS, and TPW. The
higher moisture content of the PB feedstock compared to the
WS feedstock (Table 2) does not imply a higher aqueous-phase
production. As shown in Fig. 6a, after adding the TPW to the
two biomasses, the aqueous phase yield of the PBeTPW and
WSeTPW mixtures decreased. The aqueous phase was close
to values (21 %e36%) reported in the literature for intermedi-
ate pyrolysis [11,43].
The presence of water in a pyrolysis fuel is not recom-
mended because it lowers the calorific value, adiabatic flame
temperature, and burning velocity. Fig. 6b and c displays the
contents of C, H, and N in the aqueous phase formed from the
pyrolysis and co-pyrolysis of the studied samples. It should be
highlighted that there is no information (based on a literature
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4
review) about the contents of C, H, and N in the aqueous phase
(also called the aqueous condensate). The TPW sample had a C
content of 22.43%, which was the most favourable, followed
by the WS (19.25% C) and PB (11.93% C) samples. Next, in the
aqueous phases from the co-pyrolysis of the 75PBe25TPW and
75WSe25TPW samples, the percentage of C remained essen-
tially unchanged compared to the samples without TPW.
When the TPW content was >50% of the sample mass, the
C content in the aqueous phase clearly increased. Moreover, a
trend of H reduction was observed with the addition of TPW to
the PB and WS feedstocks. It should be emphasised, however,
Fig. 6 e Aqueous phase: a) yield, and ultimate analysis
from the co-pyrolysis b) PBeTPW and c) WSeTPW.
11687
that in both cases (Fig. 6b and c), the reduction in the H con-
tent was relatively small, from approximately 10%e8.6%. A
negligible amount of N (0.15% and 0.13%) was determined only
in the aqueous phase from the pyrolysis of WS and
75WSe25TPW, respectively.
Tar and wax
Yield and ultimate analysis
Tar and wax were collected simultaneously from the first
condenser, as shown in Fig. 1. Much attention has been given
Fig. 7 e Tars and wax: a) yield, and ultimate analysis from
the co-pyrolysis of b) PBeTPW and c) WSeTPW.
11688 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4

in the literature to tar compounds produced during the pyrol-
ysis process, while the presence of wax has only been reported
in a few studies [23,35,44]. The formation of tar compounds
and wax complicated the pyrolysis process and liquid-phase
collection. The tar and wax tended to block the condensate
lines. For this reason, each campaign could not exceed 20
samples weighing 1 g. The estimated error due to tars and wax
condensation on the pipe in the second cooling zone was about
7% by mass. Siddiqui et al. [44] suggested the use of a catalyst to
reduce wax formation. Fig. 7a shows how the addition of TPW
to the PB and WS feedstocks impacted the yields of tar and
wax. The least amounts of tar and wax were formed from the
pyrolysis of PB, and the difference in the sum of tar and wax
between the PB and TPW feedstocks was 9% by mass, while
that for the WS and TPW feedstocks was approximately 5.5%.
The ultimate analysis of tar and wax compounds are
presented in Fig. 7b and c. Tarry compounds and wax from
WS had a C content of 47.22%, which was up 8.42% more than
that of PB. When 25% TPW was added to the PB and WS
feedstocks, the C contents increased to 49.61% and 54.61%,
respectively. Positive correlations between the H content and
the addition of TPW to the two types of biomass was noted.
The TPW tar and wax had the highest C and H contents, and
were also free of N. Therefore, the migration of N from the
pyrolysis atmosphere to the ta and wax was excluded. How-
ever, the N from each biomass was distributed to the chars,
aqueous phase, tar, and wax. It was clearly visible in the case
of the WS samples, where the chars and wax contained the
highest N content (0.62%).
Compounds
Tars are complex organic mixtures consisting of different
organic compounds, such as hydrocarbons, aromatics,
oxygenated, and aliphatic compounds [45,46]. Light waxes

Fig. 8 e Peak areas for selected compounds of tars and waxes from PBeTPW co-pyrolysis: a) 1-hexadecene; b) 1-
heptadecene; c) 1-octadecene; d) 1-nonadecene; e) 1-icosane; f) 1-henicosene; g) 1-docosene; h) 1-tricosene; i) tetracosane.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4 11689

(hydrocarbons C21eC40) are constitutive products of the py-
rolysis of polyolefins (low- and high-density polyethylene, and
polypropylene) [35]. Fifty-eight compounds were identified in
the tars and waxes obtained from the pyrolysis of all samples.
The most important components (by their ACD/IUPAC names)
are shown in Figs. 8 and 9.
C16eC24 alkenes with one double bond were identified in
tars and waxes from the PBeTPW samples. The addition of
TPW to PB had a clear impact on the relative proportions of
C16eC24 hydrocarbons. The following tendencies were
observed: i) the relative proportions of C16eC17 hydrocarbons
exhibited an overall increase with the increase in the mass
percent of TPW (Fig. 8a and b); ii) the maximum proportions of
C18eC21 hydrocarbons were reached at a 50% addition of TPW
(Fig. 8cef); iii) the relative proportions of C22eC24 exhibited an
overall decrease with the increase in the mass percent of TPW
from 0% to 100% (Fig. 8gei).
The main component of the tars and waxes from WS py-
rolysis was acetic acid (Fig. 9a). Acetic acid is mainly derived
from the deacetylation of hemicellulose and the degradation
of holocellulose (cellulose and hemicellulose) [47]. Lignin also
contributes to the production of minor amounts of acetic acid
and hydrocarbons by cracking the lignin side-chain [48].
Phenolic compounds, such as o-cersol, p-cresol, and 4-
ethylphenol, which belong to an aromatic group, were the
most prevalent species in tars and waxes from the WSeTPW
samples. The decomposition of the lignin present in the
biomass was responsible for the formation of phenolic com-
pounds in tar [36]. However, this was not confirmed in
Fig. 9cee because the WSeTPW feedstock lost a certain

Fig. 9 e Peak areas for selected compounds of tars and wax from WSeTPW co-pyrolysis: a) acetic acid; b) 2-vinylfuran; c) o-
cresol; d) p-cresol; e) 4-ethylphenol; f) 1,6-anhydro-b-D-glucopyranose; g) 1-nonadecene; h) 1-icosene; i) 1-docosene.
11690 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4

amount of lignin (Table 2). Phenols are combustible organics

that provide good combustibility of biofuels [43]. The same
three alkenes (1-nonadecene, 1-icosene, and 1-docosene)
were identified in tars and waxes from the PBeTPW and
WSeTPW pyrolysis samples. Interestingly, completely
different change trends in the relative proportions of these
alkenes can be observed when comparing Fig. 8deg with
Fig. 9gei.
Moreover, organic N compounds such as 1-methyl-1H-
imidazole and 4-methylpyrimidine were only identified in the

Fig. 11 e Evolution of a) CO, b) CxHy, and c) CO2

concentrations during the co-pyrolysis of WSeTPW.

Table 3 e Main hydrocarbon components from PB, WS,

TPW, PBeTPW and WSeTPW co-pyrolysis.
Sample Concentration (vol. %)
CH4 C2H2 C2H4 C2H6 C3H6 n-C4H10
PB 82.16 1.44 7.85 1.82 5.45 0.40
50PBe50TPW 82.36 1.01 7.94 4.43 3.54 0.26
TPW 84.74 0.41 7.93 4.86 1.65 0.18
Fig. 10 e Evolution of a) CO, b) CxHy, and c) CO2 50WSe50TPW 77.57 1.94 11.20 2.22 5.95 0.38
WS 61.21 0.56 25.39 11.63 0.94 0.09
concentrations during the co-pyrolysis of PBeTPW.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4 11691

residence time of the samples heated to 600  C in the hori-

Table 4 e Hydrogen content of pyrolysis gas and co-
pyrolysis gas.
Sample H2 (vol. %)
PB
50PBe50TPW
TPW
50WSe50TPW
WS
tars and waxes of the WS and WSeTPW samples. Concluding,
the TPW has a positive effect on the reduction of longer-chain
hydrocarbons and increasing the content of lower-chain hy-
drocarbons. This is in line with the conclusions of Wu and co-
workers [49,50], that the major hydrocarbons from the Tetra
Pak pyrolysis and paper pyrolysis were s 1-rings, С10-12, lev-
oglucosan, С13-15, and С16-18 components.
Gas
Figs. 10 and 11 plot the time evolution of the CO, CxHy, and CO2
concentrations of the PBeTPW and WSeTPW samples. The
zontal fixed-bed reactor was exactly 300 s. It should be
mentioned that after a sample was moved to the cooling zone,
gases still evolved from it for approximately 80 s. At a sample
9.23 temperature of approximately 280  C, the evolution of the gas
14.41 disappeared. Figs. 10 and 11 present the CO and CxHy, CO2
16.38
concentrations when gases were diluted with N2, as described
12.82
11.10
in Section Experimental stand with a fixed-bed reactor. As can
be seen in Figs. 10a and 11a, the curves representing the CO
concentration presented a maximum value (areas exposed by
magnification), which was within the time range from 84 s (for
50WSe50TPW) to 126 s (for 75PBe25TPW). To estimate the CO,
CxHy, and CO2 concentrations in the gaseous phase, the areas
under the curves were calculated (the values are presented in
the legend). The CO concentration of TPW pyrolysis was the
highest among all studied cases, while it was lowest for PB
pyrolysis.
Only the CxHy concentration (Figs. 10b and 11b) increased
practically linearly, reaching the maximum peak at an early
point (after 42 s for gas from TPW, and 70 s for gas from PB,
WS, and 75Be25TPW). At the same time, TPW gas exhibited

Fig. 12 e Carbon and hydrogen distributions in products from the co-pyrolysis of a, b) PBeTPW, and c, d) WSeTPW.
11692 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4
the highest CxHy peak. A second concentration peak was
detected in the TPW and TPW-rich mixtures.
Figs. 10c and 11c show that the CO2 concentration curves for
all investigated samples included two local maxima. In all
cases, the first maximum was clearly higher than the second.
Moreover, the instantaneous CO2 concentrations of the
WSeTPW sample were higher than those of the PBeTPW
sample. To make Figs. 10c and 11c more readable, different
scales have been used. The calculated values of the areas under
the curves showed that the addition of TPW to PB caused an
increase in the CO2 concentration of the pyrolysis gas, while
the opposite tendency was observed after adding TPW to WS. It
is also worth noting that, of all the feedstocks, the fastest re-
ductions in CO2, CO, and CxHy concentrations were for the gas
from TPW. This suggests that the TPW pyrolysis process ended
earlier in comparison to the other studied samples.
Few scientists have studied the evolution of gas concen-
trations based on the pyrolysis process time [51e53]. To the
authors’ knowledge, local peak concentration of the compo-
nents in pyrolysis gas have not been previously reported.
The analysis of hydrocarbons for selected samples are listed
in Table 3. As expected, the main hydrocarbon component (by
content) was CH4, which was followed by ethene (C2H4). The
addition of TPW to co-pyrolysis of studied biomasses influenced
differently. For WS it was spectacular, whereas for PB the effects
was little. Ethene constituted as many as 25.39% of all hydro-
carbons observed in the gas from WS pyrolysis. Jun et al. [5] also
found a high C2H4 content in syngas from WS. In the present
study, a positive correlation was observed between the addition
of TPW and the increase in the CH4 content of the pyrolysis gas.
Table 4 presents the H2 concentration of gas from the co-
pyrolysis PBeTPW and WSeTPW. The H2 concentration of gas
from PB and WS pyrolysis was lower than that of TPW pyroly-
sis, suggesting that TPW addition promoted H2 formation. The
increased release of H2 might have been related to the presence
of Al foil in the TPW because Al acts as a catalyst. Previous
studies have shown that Al powder addition to biomass accel-
erated the release of H2 during catalytic pyrolysis [54].
The H2 concentration of the pyrolysis gas was relatively
high, especially in comparison to values reported in the
literature. For instance, a study found that at temperatures of
<527  C (i.e., relatively low for pyrolysis), the production of H2
was negligible for various types of biomass [38]. Dehydroge-
nation reactions are the primary H2 source in syngas gener-
ated when the biomass pyrolysis temperature ranges from
500  C to 800  C [5].
Distribution of carbon and hydrogen in co-pyrolysis
products
The distributions of C and H in char, tar, wax, aqueous phase,
and gas were analysed. The results are shown in Fig. 12aed,
which shows that the PB char had the highest C content (59%
mass), whereas WS char had the lowest C content (38% mass).
A similar C content in a biomass char (60%) was reported Wen
et al. [15].
Apart from char, the C content in the gas phase was rela-
tively high. The percentage of C in the pyrolysis gas increased
with the increase in the TPW content in both types of biomass.
When the TPW content was >25% in the PBeTPW and
WSeTPW samples, more C was stored in the gas than in the
char. Assessing the H distribution presented in Fig. 12c and d,
it can be seen that as much as 56% of the mass of H went to the
water phase during WS pyrolysis. After adding TPW to PB and
WS, the H content in the aqueous phase reduced, while the
percentage of H in the gas phase increased.
Conclusions
In this study, the intermediate co-pyrolysis of PB and WS with
TPW was carried out in a fixed-bed reactor at 600  C. It was
shown that the addition of TPW to these two biomasses
influenced the following:

A reduction in the C content of the char and aqueous
phases owing to a decrease in the solid and aqueous
phases.

The promotion of tar and wax formation, mainly due to the
presence of LDPE (from TPW).

An increase in the distribution of C and H in gas.

An increased content of the calorific components of gas
(i.e., CO, CxHy, and H2).
Moreover, the PB, WS, and TPW chars had higher ignition
and burnout temperatures than the raw feedstocks. The
analysis results of tars and waxes showed that it is possible
to exclude N2 migration from the pyrolysis atmosphere. The
source of the N present in the tars and waxes was that
contained in the fuel. The TPW was found as a beneficial
additive for biomass intermediate co-pyrolysis, because it
reduced the long-chain hydrocarbons formation in tars, and
waxes.
In situ measurements of gas allowed us to conclude that: i)
curves showing the CO2 concentration as a function of time
presented two local maxima, regardless of the type of sample;
ii) the CxHy concentration increased almost linearly, reaching
the maximum peak after 42e70 s depending on the type of
sample. Chromatographic analysis confirmed that the main
hydrocarbon component was CH4, while the second compo-
nent in terms of content was C2H4.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This project received funding from the European Union’s
Horizon 2020 Research and Innovation Programme under a
Marie Skłodowska-Curie grant (No 823745).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4 11693

references [16] Wu C, Budarin VL, Gronnow MJ, De Bruyn M, Onwudili JA,

Clark JH, et al. Conventional and microwave-assisted
pyrolysis of biomass under different heating rates. J Anal
Appl Pyrolysis 2014;107:276e83. https://doi.org/10.1016/
[1] Sobek S, Werle S. Solar pyrolysis of waste biomass: Part 1
j.jaap.2014.03.012.
reactor design. Renew Energy 2019;143:1939e48. https://
[17] Yang Y, Brammer JG, Wright DG, Scott JA, Serrano C,
doi.org/10.1016/j.renene.2019.06.011.
Bridgwater AV. Combined heat and power from the
[2] Gao N, Li A, Quan C, Gao F. Hydrogen-rich gas production
intermediate pyrolysis of biomass materials: performance,
from biomass steam gasification in an updraft fixed-bed
economics and environmental impact. Appl Energy
gasifier combined with a porous ceramic reformer. Int J
2017;205:1610. https://doi.org/10.1016/j.apenergy.2017.08.020.
Hydrogen Energy 2008;33:5430e8. https://doi.org/10.1016/
[18] Torri C, Fabbri D. Biochar enables anaerobic digestion of
j.ijhydene.2008.07.033.
aqueous phase from intermediate pyrolysis of biomass.
[3] Azargohar R, Nanda S, Kozinski JA, Dalai AK, Sutarto R.
Bioresour Technol 2014;172:335e41. https://doi.org/10.1016/
Effects of temperature on the physicochemical
j.biortech.2014.09.021.
characteristics of fast pyrolysis bio-chars derived from
[19] Park C, Lee N, Kim J, Lee J. Co-pyrolysis of food waste and
Canadian waste biomass. Fuel 2014;125:90e100. https://
wood bark to produce hydrogen with minimizing pollutant
doi.org/10.1016/j.fuel.2014.01.083.
emissions. Environ Pollut 2020;270(1 Feb):116045. https://
[4] Gao N, Li A, Quan C, Qu Y, Mao L. Characteristics of
doi.org/10.1016/j.envpol.2020.116045.
hydrogen-rich gas production of biomass gasification with
[20] Farooq MZ, Zeeshan M, Iqbal S, Ahmed N, Shah SAY.
porous ceramic reforming. Int J Hydrogen Energy
Influence of waste tire addition on wheat straw pyrolysis
2012;37:9610e8. https://doi.org/10.1016/
yield and oil quality. Energy 2018;144:200e6. https://doi.org/
j.ijhydene.2012.03.069.
10.1016/j.energy.2017.12.026.
[5] Jun Z, Shuzhong W, Zhiqiang W, Haiyu M, Lin C. Hydrogen-rich  nı́ odpadnı́ho materia  lu Tetra
[21] Pavlik P. Pyrolýznı́ zpracova
syngas produced from the co-pyrolysis of municipal solid   Univerzita Ostrava; 2018.
Pak. Thesis. VSB-Technick a
waste and wheat straw. Int J Hydrogen Energy 
[22] Haydary J, Susa D, Duda s J. Pyrolysis of aseptic packages
2017;42:19701e8. https://doi.org/10.1016/j.ijhydene.2017.06.166.
(tetrapak) in a laboratory screw type reactor and secondary
[6] Zhu J, Zhu L, Guo D, Chen Y, Wang X, Zhu Y. Co-pyrolysis of
thermal/catalytic tar decomposition. Waste Manag
petrochemical sludge and sawdust for syngas production by
2013;33:1136e41. https://doi.org/10.1016/
TG-MS and fixed bed reactor. Int J Hydrogen Energy
j.wasman.2013.01.031.
2020;45:30232e43. https://doi.org/10.1016/
[23] Korkmaz A, Yanik J, Brebu M, Vasile C. Pyrolysis of the tetra
j.ijhydene.2020.08.092.
pak. Waste Manag 2009;29:2836e41. https://doi.org/10.1016/
[7] Demirbas‚ A, Arin G. An overview of biomass pyrolysis.
j.wasman.2009.07.008.
Energy Sources 2002;24:471e82. https://doi.org/10.1080/
[24] Huo H, Ma Y. TG/DTA-FTIR study on total resource recovery
00908310252889979.
from Tetra Pak waste by pyrolysis under a CO2 environment.
[8] Bridgwater AV. Review of fast pyrolysis of biomass and
Prog React Kinet Mech 2018;43:229e35. https://doi.org/
product upgrading. Biomass Bioenergy 2012;38:68e94.
10.3184/146867818X15233705894437.
https://doi.org/10.1016/j.biombioe.2011.01.048.
[25] Wang Z, Burra KG, Zhang M, Li X, Policella M, Lei T, et al. Co-
[9] Liu C, Wang H, Karim AM, Sun J, Wang Y. Catalytic fast
pyrolysis of waste tire and pine bark for syngas and char
pyrolysis of lignocellulosic biomass. Chem Soc Rev
production. Fuel 2020;274. https://doi.org/10.1016/
2014;43:7594e623. https://doi.org/10.1039/c3cs60414d.
j.fuel.2020.117878.
[10] Tripathi M, Sahu JN, Ganesan P. Effect of process parameters
[26] Brebu M, Ucar S, Vasile C, Yanik J. Co-pyrolysis of pine cone
on production of biochar from biomass waste through
with synthetic polymers. Fuel 2010;89:1911e8. https://
pyrolysis: a review. Renew Sustain Energy Rev
doi.org/10.1016/j.fuel.2010.01.029.
2016;55:467e81. https://doi.org/10.1016/j.rser.2015.10.122.  czyk A.
[27] Mirowski T, Mokrzycki E, UliaszeBochen
[11] Funke A, Tomasi Morgano M, Dahmen N, Leibold H.  w: IGSMiE PAN
Energetyczne wykorzystanie biomasy. Krako
Experimental comparison of two bench scale units for fast
e Wydawnictwo; 2018.
and intermediate pyrolysis. J Anal Appl Pyrolysis € z S. Influence of co-pyrolysis of waste
[28] Tekin K, Ucar S, Karago
2017;124:504e14. https://doi.org/10.1016/j.jaap.2016.12.033.
tetra pak with waste motor oil on product distribution and
[12] Hornung A, Apfelbacher A, Sagi S. Intermediate pyrolysis: a
properties for fuel application. Energy Fuels
sustainable biomass-to-energy concept-biothermal
2019;33:11101e12. https://doi.org/10.1021/
valorisation of biomass (BtVB) process. J Sci Ind Res (India)
acs.energyfuels.9b02634.
2011;70:664e7.
[29] Soest PJ Van. Use of detergents in the analysis of fibrous
[13] Yang Y, Brammer JG, Mahmood ASN, Hornung A.
feeds. II. A rapid method for the determination of fiber and
Intermediate pyrolysis of biomass energy pellets for
lignin. J AOAC Int 1990;73:491e7. https://doi.org/10.1093/
producing sustainable liquid, gaseous and solid fuels.
jaoac/73.4.491.
Bioresour Technol 2014;169:794e9. https://doi.org/10.1016/ €
€ r A, Onenç
[30] Güngo S, Uçar S, Yanik J. Comparison between the
j.biortech.2014.07.044.
“one-step” and “two-step” catalytic pyrolysis of pine bark. J
[14] Mahmood ASN, Brammer JG, Hornung A, Steele A,
Anal Appl Pyrolysis 2012;97:39e48. https://doi.org/10.1016/
Poulston S. The intermediate pyrolysis and catalytic steam
j.jaap.2012.06.011.
reforming of Brewers spent grain. J Anal Appl Pyrolysis € r S, Hemming J,
[31] Valentı́n L, Kluczek-Turpeinen B, Willfo
2013;103:328e42. https://doi.org/10.1016/j.jaap.2012.09.009.
Hatakka A, Steffen K, et al. Scots pine (Pinus sylvestris) bark
[15] Wen Y, Wang S, Mu W, Yang W, Jo € nsson PG. Pyrolysis
composition and degradation by fungi: potential substrate
performance of peat moss: a simultaneous in-situ thermal
for bioremediation. Bioresour Technol 2010;101:2203e9.
analysis and bench-scale experimental study. Fuel
https://doi.org/10.1016/j.biortech.2009.11.052.
2020;277:118173. https://doi.org/10.1016/j.fuel.2020.118173.
11694 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 1 6 8 0 e1 1 6 9 4
[32] Ding T, Li S, Xie J, Song W, Yao J, Lin W. Rapid pyrolysis of
wheat straw in a bench-scale circulating fluidized-bed
downer reactor. Chem Eng Technol 2012;35:2170e6. https://
doi.org/10.1002/ceat.201200140.
[33] Demirbas A. Combustion characteristics of different biomass
fuels. Prog Energy Combust Sci 2004;30:219e30. https://
doi.org/10.1016/j.pecs.2003.10.004.
[34] Li Q, Zhao C, Chen X, Wu W, Li Y. Comparison of pulverized
coal combustion in air and in O2/CO2 mixtures by thermo-
gravimetric analysis. J Anal Appl Pyrolysis 2009;85:521e8.
https://doi.org/10.1016/j.jaap.2008.10.018.
[35] Arabiourrutia M, Elordi G, Lopez G, Borsella E, Bilbao J,
Olazar M. Characterization of the waxes obtained by the
pyrolysis of polyolefin plastics in a conical spouted bed
reactor. J Anal Appl Pyrolysis 2012;94:230e7. https://doi.org/
10.1016/j.jaap.2011.12.012.
[36] Magdziarz A, Wilk M, Wa˛drzyk M. Pyrolysis of hydrochar
derived from biomass - experimental investigation. Fuel
2020;267:117246. https://doi.org/10.1016/j.fuel.2020.117246.
[37] Jerzak W. Effect of pine bark combustion temperature on
content of major, minor, and trace elements in ashes:
experimental study and thermodynamic equilibrium
calculations. J Energy Eng 2020;146:04019031. https://doi.org/
10.1061/(ASCE)EY.1943-7897.0000632.
[38] Di Blasi C, Signorelli G, Di Russo C, Rea G. Product
distribution from pyrolysis of wood and agricultural
residues. Ind Eng Chem Res 1999;38:2216e24. https://doi.org/
10.1021/ie980711u.
[39] International Biochar Initiative. Standardized product
definition and product testing guidelines for biochar that is
used in soil. Prod Defin Specif Stand 2015:1e61. http://www.
biochar-international.org/sites/default/files/Guidelines_for_
Biochar_That_Is_Used_in_Soil_Final.pdf.
[40] Sanchez-Silva L, Lo  pez-Gonza  lez D, Villasen
~ or J, Sa
 nchez P,
Valverde JL. Thermogravimetric-mass spectrometric
analysis of lignocellulosic and marine biomass pyrolysis.
Bioresour Technol 2012;109:163e72. https://doi.org/10.1016/
j.biortech.2012.01.001.
[41] Figen AK, Terzi E, Yilgo € r N, Kartal SN, Pis‚kin S. Thermal
degradation characteristic of Tetra Pak panel boards under
inert atmosphere. Kor J Chem Eng 2013;30:878e90. https://
doi.org/10.1007/s11814-012-0185-y.
[42] Grotkjær T, Dam-Johansen K, Jensen AD, Glarborg P. An
experimental study of biomass ignition. Fuel 2003;82:825e33.
https://doi.org/10.1016/S0016-2361(02)00369-1.
[43] Santos J, Ouadi M, Jahangiri H, Hornung A. Integrated
intermediate catalytic pyrolysis of wheat husk. Food Bioprod
View publication stats
Process 2019;114:23e30. https://doi.org/10.1016/
j.fbp.2018.11.001.
[44] Siddiqui MZ, Han TU, Park YK, Kim YM, Kim S. Catalytic
pyrolysis of tetra pak over acidic catalysts. Catalysts
2020;10:602. https://doi.org/10.3390/catal10060602.
[45] Amini E, Safdari MS, DeYoung JT, Weise DR, Fletcher TH.
Characterization of pyrolysis products from slow pyrolysis of
live and dead vegetation native to the southern United
States. Fuel 2019;235:1475e91. https://doi.org/10.1016/
j.fuel.2018.08.112.
[46] Ben H, Wu F, Wu Z, Han G, Jiang W, Ragauskas AJ. A
comprehensive characterization of pyrolysis oil from
softwood barks. Polymers 2019;11:1387. https://doi.org/
10.3390/polym11091387.
[47] Dong CQ, Zhang ZF, Lu Q, Yang YP. Characteristics and
mechanism study of analytical fast pyrolysis of poplar wood.
Energy Convers Manag 2012;57:49e59. https://doi.org/
10.1016/j.enconman.2011.12.012.
[48] Bertero M, Gorostegui HA, Orrabalis CJ, Guzma  n CA,
Calandri EL, Sedran U. Characterization of the liquid
products in the pyrolysis of residual chan~ ar and palm fruit
biomasses. Fuel 2014;116:409e14. https://doi.org/10.1016/
j.fuel.2013.08.027.
[49] Wu CH, Chang HS. Pyrolysis of tetra pack in municipal solid
waste. J Chem Technol Biotechnol 2001;76:779e92. https://
doi.org/10.1002/jctb.404.
[50] Wu CH, Chang CY, Tseng CH. Pyrolysis products of uncoated
printing and writing paper of MSW. Fuel 2002;81:719e25.
https://doi.org/10.1016/S0016-2361(01)00180-6.
[51] Gautam R, Shyam S, Reddy BR, Govindaraju K, Vinu R.
Microwave-assisted pyrolysis and analytical fast pyrolysis of
macroalgae: product analysis and effect of heating
mechanism. Sustain Energy Fuels 2019;3:3009e20. https://
doi.org/10.1039/c9se00162j.
[52] Silva RB, Martins-Dias S, Arnal C, Alzueta MU, Costa M.
Pyrolysis and char characterization of refuse-derived fuel
components. Energy Fuels 2015;29:1997e2005. https://
doi.org/10.1021/ef502011f.
[53] Yao D, Wu C, Yang H, Zhang Y, Nahil MA, Chen Y, et al. Co-
production of hydrogen and carbon nanotubes from catalytic
pyrolysis of waste plastics on Ni-Fe bimetallic catalyst.
Energy Convers Manag 2017;148:692e700. https://doi.org/
10.1016/j.enconman.2017.06.012.
[54] Liu P, Wang Y, Zhou Z, Yuan H, Zheng T. Gas fuel production
derived from pine sawdust pyrolysis catalyzed on alumina.
Asia Pac J Chem Eng 2020;15:1e11. https://doi.org/10.1002/
apj.2456.