Journal of Hazardous Materials 468 (2024) 133724

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Journal of Hazardous Materials

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A comparative study of the pyrolysis and hydrolysis conversion of tire

Likun Wang , Xiaochao Wang , Jie Yu *
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, 430074 Wuhan, Hubei, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Higher temperatures can promote the

formation of aromatics.
• Hydrolysis promote the early release of
nitrogen-containing compounds.
• Higher hydrolysis temperatures can
promote the formation of sulfide.
• Temperature has a weak effect on oil
composition for pyrolysis process.
• Extensive of NxOy, NxOySz, NxSy, Nx
and Ox classes formed.

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

Keywords: In the present study, we pyrolyzed a waste tire at various temperatures under an N2 atmosphere and a water
Hydrolysis environment in an autoclave reactor to investigate the effect of water on tire degradation. The analysis involved a
Pyrolysis comparison of product distribution, char properties, oil composition, and the behavior of heteroatom elements
Tire
(especially oxygen, nitrogen, and sulfur) under different atmospheres. Elemental analysis, functional-group
FT-ICR MS
identification, and chemical state analysis of sulfur were performed for chars. In addition, the chemical
Hetero-compound
composition, elemental composition, and molecular weight of the produced oils were evaluated. The heavy
fraction of oils, not detectable by gas chromatography-mass spectrometry (GC-MS), was analyzed through
Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The findings revealed that high
temperatures promoted oil cracking, resulting in the formation of light oils in both pyrolysis and hydrolysis
processes. Compared to pyrolysis, hydrolysis generated a higher yield of low molecular–weight oil. Elevated
hydrolysis temperatures promoted aromatization, yielding an oil with a low H/C ratio and a high double bond
equivalent number. Consequently, the concentration of aromatics in the light fraction of oils generated from the
hydrolysis process exceeded that in oils from the pyrolysis process. Temperature exhibited a limited impact on oil
composition during the pyrolysis process. Hydrolysis promoted the release of heteroatom-containing compounds
at low temperatures. During pyrolysis, nitrogen was gradually released from the solid phase, whereas nitrogen-
containing compounds were released early during hydrolysis, with gas-phase nitrogen accounting for more than
50 wt% at 320 ◦ C. A maximum D-limonene yield of 45.58% was obtained at 360 ◦ C within 0 min of hydrolysis,

* Corresponding author.
E-mail address: [email protected] (J. Yu).

https://doi.org/10.1016/j.jhazmat.2024.133724
Received 1 November 2023; Received in revised form 29 January 2024; Accepted 3 February 2024
Available online 7 February 2024
0304-3894/© 2024 Elsevier B.V. All rights reserved.
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

with the potential conversion of D-limonene into aromatics at higher hydrolysis temperatures. These results
contribute to the understanding of tire valorization via hydrolysis.

1. Introduction alkenes, aromatics, and alkyls. Another study on depolymerization of

styrene–butadiene rubber in near-critical and supercritical water in the
Research on tire valorization has gained significant traction recently presence of H2O2 [28] demonstrated the dominance of oxidative and
owing to its extensive application and the intrinsic value of rubber, a key thermal degradation at low and high temperatures, respectively.
constituent of tires. According to global estimations, nearly 1.5 billion Hydrogen radicals can participate in the stabilization of intermediates
tires are disposed of annually because of the rapid growth of automo­ formed during rubber decomposition, therefore impeding the recombi­
biles [1]. Tires mainly consist of rubber, steel, and black carbon. During nation reaction [6]. Zhang et al. also investigated the impact of atmo­
tire manufacturing, rubber undergoes vulcanization using sulfur vulca­ sphere, temperature, pressure, time, and water-to-sample ratio on
nizing agents and accelerators to enhance the properties of the tire [2]. product distribution [22]. H2 and CO environments were conducive to
Other additives, such as processing oils, stabilizers, and antioxidants the production of oil with high flowability. Oil derived from hydro­
(such as stearic acid), are also incorporated to optimize the properties of thermal treatment reportedly exhibited a low concentration of oxygen,
tires [3]. Consequently, tires exhibit high concentrations of sulfur, ni­ but was rich in nitrogen and sulfur, necessitating additional treatments.
trogen, and oxygen. Although previous studies affirm the feasibility of recycling tires
In recent years, chemical recycling methods, such as pyrolysis, using the hydrolysis method, the evolution of heteroatom compounds is
gasification, and hydrothermal treatment, have been extensively studied rarely analyzed. Additionally, to the best of our knowledge, a compar­
for tire valorization [3–8]. Pyrolysis of tires is one of the most attractive ative analysis of the pyrolysis and hydrolysis processes using a bench-
ways to recycle oil and black carbon. During the pyrolysis process, ad­ scale reactor has not been undertaken. Therefore, in the present study,
ditives and rubber decompose, mainly forming oil, while black carbon we pyrolyzed a waste tire under an N2 atmosphere and water environ­
stays as char. The pyrolysis behavior of tires is influenced by numerous ment in an autoclave reactor. The object was to unveil the effect of water
factors such as temperature, residence time, and reactor type [9–11]. on tire degradation by comparing the product distribution, char char­
Typically, elevated temperatures can promote the decomposition of acteristics, oil composition, and the behavior of heteroatom elements,
rubber, leading to a substantial increase in oil formation, while high especially those of oxygen, nitrogen, and sulfur.
temperatures can result in increased gas formation owing to secondary
reactions, which occur in most reactors [12]. As the temperature in­ 2. Experimental
creases from 300 to 700 ◦ C, the liquid yield, for instance, increases from
4.8 to 38.5 wt% [13]. Previously, 500 ◦ C was suggested as the optimum 2.1. Materials
temperature for tire pyrolysis. High heating rates can drive sulfur
migration into volatiles [11] and encourage the formation of isoprene The sample used in this study was prepared by shredding and
trimers [10]. grinding an automobile tire after removing steel. The results of
Pyrolytic tire oil is composed of aromatic, aliphatic, and undesired elemental and proximate analyses of the sample are shown in Table 1.
heteroatom compounds. The aromatic and aliphatic compounds are The ash content in the table represents the inorganic additives incor­
produced from rubber decomposition [14], while the heteroatom com­ porated during the manufacturing process, while the fixed carbon is
pounds are mainly derived from the decomposition of the vulcanization predominantly composed of black carbon. Additionally, the presence of
accelerators, antioxidants, plasticizers, and tire cord fibers [15]. During oxygen, sulfur, and nitrogen in the tire sample indicated the existence of
the pyrolysis process, an aromatization reaction occurs between the cross-linking agents, stabilizers, and other secondary components [27].
poly-aromatic hydrocarbons and sulfur, with this reaction being accel­
erated at high temperatures [16]. In our previous study, we evaluated
2.2. Experimental setup
the effect of H2S on rubber decomposition via molecular dynamic sim­
ulations and experiments. H2S was found to promote dehydrogenation,
A Hastelloy alloy autoclave reactor with an internal volume of 100
leading to the formation of poly-aromatic compounds and extra
mL, capable of operating up to 500 ◦ C and 30 MPa, was used to conduct
sulfur-containing compounds such as phenylthiophene and dibenzo­
our experiments. A schematic of the reactor device is displayed in
thiophene [17].
Figure SM-1. The autoclave reactor was heated by an electric furnace
Hydrolysis, as an alternative method for recycling tires, occurs in an
and cooled by a fan. The effect of temperature was analyzed at target
aqueous environment. Extensive studies have been conducted to up­
temperatures of 320, 360, 410, and 460 ◦ C. To evaluate the effect of
grade various materials, including coal, biomass, plastic, tire, and heavy
reaction time, specifically, the duration required by the reactor to sus­
oils, under aqueous conditions [18–25]. Despite decomposition in an
tain a reaction after reaching the target temperature, two residence
aqueous phase being influenced by different reaction conditions (such as
times of 0 and 60 min were chosen for the experiments. In the case of the
temperature, pressure, and reaction time), water has been suggested as a
hydrolysis, 30 mL of H2O was loaded into the autoclave reactor before
suitable medium for accelerating tire decomposition under conditions
the experiment. The reactor was then purged with N2 through pressur­
milder than those involved in pyrolysis [22]. A comparison between
ization/depressurization. Depending on the target temperature, final
pyrolysis and hydrothermal treatment [26] reveals that, in contrast to
pressures of up to ~7, 10, 16, and 18 MPa were attained at 320, 360,
hydrothermal treatment, nine hours of pyrolysis results in the formation
410, and 460 ◦ C, respectively. To make a comparison and assess the
of a larger amount of solid residue. Li et al. carried out thermolysis of
impact of the reaction atmosphere, H2O was substituted with N2. During
tires and rubber in subcritical and supercritical water using a batch
the ramping period, the time required to reach the target temperature
tubular reactor [27]. A maximum oil yield of 21.21% was obtained at
the near-critical point, with the yield decreasing at higher temperatures
and pressures. Ahmad et al. explored hydrous pyrolysis of natural rubber Table 1
Ultimate and proximate analysis results of the sample tire.
to produce oils at various temperatures, reaction times, and
water-to-rubber ratios [24]. A maximum oil yield of 76 wt% was ob­ Proximate analysis (air-dry basis) Ultimate analysis (dry basis)
tained at 375 ◦ C for 30 min of pyrolysis conducted with a Mad Aad Vad Fcad C H O S N
water-to-rubber ratio of 3:1. The resulting oil was mainly composed of 0.60 8.47 72.30 18.63 78.19 7.16 5.46 1.87 0.54

2
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

for pyrolysis was shorter than that for hydrolysis as shown in Figure SM- samples were passed through a fused-silica capillary at a rate of 360 μL
2. This result indicates that the energy required to reach the target h− 1 using a syringe pump (Hamilton Corporation). The flow rate of the
temperature and pressure was higher for hydrolysis than for pyrolysis. drying gas N2 was set as 2.0 L min− 1 at 200 ◦ C and that of the nebulizing
For the pyrolysis process, the final pressures ranged from 0.14 to 0.44 gas was 1.0 L min− 1. Peaks with a relative abundance higher than six
MPa, significantly lower than those experienced in the hydrolysis pro­ standard deviations of the baseline root-mean-square noise (6σ) were
cess. At the end of the experiments, as the furnace cooled, the liquid and used in the data analysis. The chemical formulas
solid products were collected by washing the reactor with dichloro­ (C1–100H1–200N0–8O0–8S0–4) were determined based on the m/z values,
methane. The solid was separated from the liquid using a filter funnel. with the relative deviation between the measured and theoretical m/z
The oil product was extracted from the water phase using dichloro­ values being less than 2 ppm. For the parent ions, double bond equiv­
methane as a solvent and separated using a separatory funnel. alent (DBE) was calculated as DBE = c − h/2 + n/2 + 1, where c, h, and
n indicate the numbers of C, H, and N atoms in the formulas,
2.3. Characterization respectively.

The elemental composition of solid and liquid products was analyzed 3. Results
using an elemental analyzer (Vario Micro cube). The proximate analyses
of the solid products were conducted using a thermogravimetric appa­ 3.1. Product distribution
ratus (Las Navas TGA2000). The functional groups present in the solid
products were identified using a Fourier-transform infrared spectrom­ The product distribution obtained from the thermal treatment of
eter (FTIR; VERTEX 70) within a scanned spectral range from 4000 to tires at various temperatures is presented in Fig. 1(a). A declining trend
400 cm− 1 at a resolution of 2 cm− 1. The valency of sulfur in the solid in solid residue is evident with an increase in temperature for both py­
products was determined using an X-ray photoelectron spectrometer rolysis and hydrolysis. Even though more samples are decomposed at
(XPS; Thermo Fisher ESCALAB 250Xi) equipped with a monochromatic higher temperatures, the oil yield decreases with an increase in the
Al Kα radiation source. The ash composition of the tire was analyzed temperature, especially at 410 ◦ C and above. As illustrated in Fig. 1(a),
using an X-ray diffractometer (XRD; PANalytical B.V. x′pert3 powder) hydrolysis at 320 ◦ C yields a maximum amount of 48.64 wt% of oil,
and an X-ray fluorescence spectrometer (XRF; SHIMADZU EDS-8000). which markedly drops to 41.36 wt% as the temperature increases to
The composition of oils was determined using gas chromatography- 410 ◦ C. Previous studies also showed that the oil yield tends to increase
mass spectrometry (GC–MS, Agilent 7890 A/5975 C); the spectrom­ with an increase in the temperature between 250 and 375 ◦ C during the
eter equipment was equipped with an HP-5MS column (30 m length, hydrolysis process [29,30], possibly because the reaction is kinetically
0.25 mm internal diameter, and 0.25 mm film thickness) and was pro­ controlled within this temperature range, but is retarded above
grammed to remain at 45 ◦ C for 4 min, then ramped to 300 ◦ C at a rate of 360–400 ◦ C [22,31]. The decrease in the oil yield is attributed to the
10 K min− 1, and held at 300 ◦ C for 10 min. The molecular weights of the degradation of oils into gaseous products. Below 360 ◦ C, the gas yields
produced oils were analyzed by gel permeation chromatography (GPC; are lower than 4 wt% for both treatment methods, indicating that the
EVANS Series 1500); the device was equipped with a Shodex column secondary reaction remains weak. As the temperature increases from
(KF-402.5, L: 300 mm, D: 8 mm), which was kept at 40 ◦ C with tetra­ 360 to 410 ◦ C, the gas yield significantly increases from 3.18 wt% to
hydrofuran (THF) as the mobile phase at a flow rate of 0.5 mL min− 1. 21.87 wt%. At a higher temperature of 460 ◦ C, the oil yield experiences a
The resulting UV absorbance signals at 300 nm were recorded. The slight further decrease. These results indicate that the secondary reac­
compositions of the heavy fraction of oils were determined by Fourier- tion becomes pronounced at 410 ◦ C and above. The slow ramping and
transform ion cyclotron resonance mass spectrometry (FT ICR–MS) cooling periods shown in Figure SM-1 may accelerate the secondary
analysis performed on a 15 T SolariX XR FT ICR–MS system (Bruker reaction at high temperatures.
Corp.) with atmospheric pressure photoionization (APPI) and electro­ In comparison to the hydrolysis process, the pyrolysis of a tire in an
spray ionization (ESI). Before the analysis, the oil samples were dis­ inert atmosphere results in a lower amount of oil but higher gas pro­
solved in toluene with a concentration of 0.2 mg mL− 1. The prepared duction. At 320 ◦ C, the conversion rate for the hydrolysis process is

Fig. 1. Product distribution of solid, liquid, and gas. (a) Comparison between pyrolysis and hydrolysis (0 min residence time). (b) Effect of reaction time during
hydrolysis. PY: Pyrolysis; HY: Hydrolysis.

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L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

higher than that for the pyrolysis process. As the temperature increases 3.2.2. Functional groups analysis
to 360 ◦ C, more gas is formed during the pyrolysis process possibly The functional groups in the chars produced from both pyrolysis and
because of the strong catalytic effect of the chars, leading to the cracking hydrolysis are compared in Fig. 2. The strong band at 1632 cm− 1 is
of a substantial amount of the produced oils. associated with C––C polyisoprene [33]. The bands at 2920, 2845, and
The impact of reaction time on the product distribution at various
temperatures during hydrolysis is shown in Fig. 1(b). At 320 ◦ C, the
effect of residence time on the product distribution is weak. The
amounts of the solid residue and oil slightly decrease as the residence
time increases from 0 to 60 min. This result indicates that the vulnerable
components of the organic additives and parts of the rubber may
decompose during the ramping period. As the temperature increases to
360 ◦ C, the solid residue content decreases at 60 min and becomes
similar to that obtained at 410 ◦ C and above, indicating complete
decomposition under this condition. The liquefaction at 410 and 460 ◦ C
for 0 min can produce the maximum yield of oil owing to the minimized
secondary reactions. Increasing the reaction time can decrease the oil
yield, especially at 410 ◦ C and above, possibly due to strong secondary
reactions.

3.2. Charcharacterization

3.2.1. Ultimate and proximate analyses

The results of the ultimate and proximate analyses of the chars are
presented in Table 2. Chars produced at elevated temperatures and
extended reaction times display small amounts of volatile matter,
hydrogen, and oxygen content but a substantial amount of elemental
carbon, correlating with low char yields, potentially attributed to the
accelerated decomposition reaction. Nitrogen exhibits distinct behav­
iors in pyrolysis and hydrolysis. In the pyrolysis process, the nitrogen
concentration in chars is decreased gradually with the increase in py­
rolysis temperature. The char produced at 320 ◦ C contains the highest
amount of nitrogen (0.7%), which gradually decreases to 0.4% at
460 ◦ C, suggesting the gradual decomposition of heteroatom com­
pounds containing oxygen and nitrogen during pyrolysis. Compara­
tively, the nitrogen concentration in chars from hydrolysis remains
relatively constant or even slightly increases. The nitrogen in chars
produced at 320 ◦ C is already low at around 0.3%, indicating the release
of a significant amount of nitrogen-containing compounds at this tem­
perature. However, the rest nitrogen-containing compounds resist
decomposition and survive up to 460 ◦ C. At 460 ◦ C, there is a negligible
difference in nitrogen concentration between chars produced from py­
rolysis and hydrolysis. Therefore, hydrolysis can promote the release of
nitrogen-containing compounds at lower temperature ranges. In
contrast to oxygen and nitrogen, sulfur content in solid residues in­
creases with the decomposition of tires. During the reaction, some sulfur
is retained within solid residues, forming ZnS, which is resistant to
release at higher temperatures [32].
Fig. 2. FTIR analysis results of the chars. PY: Pyrolysis; HY: Hydrolysis; e.g.,
PY-320–0: pyrolysis at 320 ◦ C for 0 min.

Table 2
Results of the ultimate and proximate analyses of the chars.
Condition Temperature Time (min) Ultimate analysis Proximate analysis
(◦ C) (wt%, daf.) (wt%, daf.)

C H O N S Volatile matter Fixed carbon

Pyrolysis 320 0 88.6 4.0 3.9 0.7 2.8 57.2 42.8

360 0 88.7 3.9 3.5 0.6 3.2 56.5 43.5
410 0 89.0 3.2 3.6 0.5 3.7 26.9 74.1
460 0 91.6 1.5 2.6 0.4 4.0 24.4 75.6
Hydrolysis 320 0 87.0 4.9 4.8 0.3 3.0 51.5 48.5
60 89.8 3.4 3.4 0.3 3.1 45.7 54.3
360 0 88.3 3.8 4.7 0.3 2.9 40.9 59.1
60 91.4 1.7 3.0 0.3 3.6 31.2 68.8
410 0 90.1 1.8 3.9 0.4 3.9 24.2 75.8
60 91.8 1.1 2.9 0.3 3.9 21.6 78.4
460 0 90.4 1.5 3.5 0.4 4.1 24.2 75.8
60 92.7 1.0 2.1 0.4 3.8 21.7 78.3

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L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

1435 cm− 1 can be assigned to C–H stretching and bending vibrations The carbon and hydrogen contents show no significant variation with
[34,35]. The band at 460 cm− 1 indicates the existence of S–S [33]. In the the change in pyrolysis temperature. As the temperature increases from
–C polyisoprene and the O–H band in the spectrum
pyrolysis process, C– 320 to 460 ◦ C, the oxygen content markedly decreases from 2.1 to
of the raw tire disappear at 320 ◦ C, and a peak corresponding to aro­ 1.1 wt%, in contrast to nitrogen and sulfur contents, which only change
matic C––C starts to form, indicating complete conversion of the rubber slightly with the temperature variation. A similar trend is observed for
components and additives. Conversely, the char from the hydrolysis hydrolysis, with the exception that the average oxygen content in oils is
process at 320 ◦ C still preserves moderate intensities of C– –C poly­ higher. At 460 ◦ C for 60 min, the oxygen in oil can reach up to 2.1 wt%.
isoprene, O–H, and C–H stretching vibration bands. The existence of Correspondingly, the lowest oxygen content of 2.1 wt% can be observed
these bands indicates that parts of rubber and additives are not liquefied. in char generated at the same condition, indicating the release of parts of
Extending reaction time from 0 to 60 min at 320 ◦ C, the C– –C poly­ oxygen-containing compounds at 460 ◦ C. Another distinct difference
isoprene and O–H band are completely diminished, but a moderate in­ between pyrolysis and hydrolysis is that the H/C is decreased with the
tensity of the C–H band is still preserved. For chars obtained from both increase in hydrolysis temperature. Specifically, the lowest H/C ratio of
pyrolysis and hydrolysis methods at 410 ◦ C and above, most bands are 1.34 can be registered for oil obtained at 460 ◦ C, indicating the stronger
diminished. dehydrogenation and aromatization reactions.

3.2.3. Chemical state of sulfur 3.3.2. Molecular weight analysis

Sulfur species are divided into two separate peaks of 2p3/2 and 2p1/2 The average molecular weights (MWs) of the oils are shown in
with a relative intensity of 2:1, binding energy gap of 1.2 eV [36], fixed Table 5, serving as an indication of trends between samples, despite the
binding energy position, and full width at half maximum value. The challenges in estimating oils due to the limitations of THF as solvent and
speciation of sulfur can be derived by deconvoluting the XPS spectra as variations in detector response to different compounds [40]. In the py­
shown in Figure SM-3. The dominating peak corresponding to a binding rolysis process, the MW of oils gradually decreases with the increase in
energy of S 2p at 162.0 ± 0.4 eV can be assigned to sulfide, mainly ZnS, temperature due to the strengthened cracking reaction at higher tem­
owing to the interaction between ZnO and H2S [37]; this result was peratures. A similar trend is also observed for hydrolysis. For the hy­
verified through X-ray diffraction analysis as shown in Figure SM-4. The drolysis with 0 min holding time, the MW of oil is markedly decreased
peak at 164.0 ± 0.4 eV corresponds to organic sulfur, such as thiophene from 1130 to 378 as the temperature increases from 320 to 460 ◦ C. At a
and alkyl sulfide groups [38], and that at ~169.4 ± 0.4 eV is associated low temperature of 320 ◦ C, the liquefaction of the tire can produce much
with sulfate, such as CaSO4 [39]. This can be supported by the compo­ heavier oil. At higher temperatures, the oils can be cracked into lighter
sition and X-ray diffraction analyses of the chars (Figure SM-4 and ones, and the re-polymerization reactions are hindered due to the “cage
Table SM-1). The area of the deconvoluted peaks represents the relative effect” of water molecules. With a longer residence time, oils exhibit a
content of different species (Table 3). For the pyrolysis process, sulfide different trend at different temperatures. At 320 and 360 ◦ C, a longer
and organic-S are the major sulfur species accounting for around 70% reaction time promotes the cracking reaction of initially formed oligo­
and 20% respectively, which are close to those reported in a previous mers, resulting in a decrease in MW of oils as the reaction progresses. At
study [38]. As the temperature increases, the relative contents of the 410 and 460 ◦ C, an opposite trend can be observed. The simulated
three sulfur species do not show notable variations. This result indicates distillation results of the oils in Figure SM-4 indicate that the oils pro­
that most sulfur atoms bonded within the cross-linked rubber partially duced at 60 min are concentrated in a narrow range. With the reaction
decompose and transform into sulfide at 320 ◦ C, while the sulfur in the proceeding at high temperatures, the heaviest compounds are cracked
organic matrix is possibly incorporated into the aromatic rings and can into relatively lighter ones, while the smaller compounds are cracked
be retained at high temperatures. At lower temperatures, the solid res­ into non-condensable fractions, consistent with the marked decrease in
idues generated from hydrolysis are composed of more organic-S and the oil yield shown in Fig. 1(b).
sulfate but less sulfide. As the temperature increases, organic-S is
gradually decomposed and transformed into sulfide. The sulfate content 3.3.3. Analysis of light fraction of oils
is higher in all the solid residues generated from hydrolysis than in those The compositions of the oils produced under various conditions are
generated from pyrolysis and remains constant as the temperature in­ shown in Table 6. The oils are categorized into aliphatic compounds,
creases. In an aqueous environment, sulfate is more easily formed owing aromatic compounds, O-containing compounds, N,O-containing com­
to the participation of H2O. pounds and S,N,O-containing compounds. Here, the N,O-containing
compounds refer to compounds with nitrogen alone or both nitrogen
3.3. Oil characterization and oxygen, while S,N,O-containing compounds include S-containing
compounds, S,N-containing compounds and compounds containing
3.3.1. Ultimate analysis sulfur, nitrogen, and oxygen. In the pyrolysis process, the aliphatic
The results of the ultimate analysis of the oils derived from the compounds dominate in oils, followed by aromatic and heteroatom-
thermal treatment of the tire at various conditions are shown in Table 4. containing compounds. The aliphatic compounds are mainly
composed of alkene, with D-limonene being the main compound,
Table 3 consistent with the results of previous studies [41]. At 360 ◦ C, the
Relative contents of sulfur-containing compounds (area.%). maximum yield of D-limonene (~22.48%) is achieved; this result elu­
Condition Temperature (◦ C) Time (min) Sulfide Organic-S Sulfate
cidates the high yield of aliphatic compounds at 360 ◦ C. As the tem­
perature increases, the yield of D-limonene decreases owing to the
Pyrolysis 320 0 69.3 22.9 7.8
transformation of D-limonene into aromatic compounds. The aromatic
360 0 71.8 20.1 8.1
410 0 70.9 21.0 8.1 compounds are classified as monocyclic aromatics, mainly including
460 0 68.1 22.0 9.9 benzene derivatives, and polycyclic aromatic hydrocarbons, mainly
Hydrolysis 320 0 43.7 39.5 16.8 comprising indene and naphthalene derivatives. For the O-compounds
60 52.0 32.1 15.9 in pyrolytic oils, the content is high and remains relatively unaffected by
360 0 48.8 34.0 17.3
60 59.1 24.7 16.2
pyrolysis temperature. These O-compounds mainly consist of acid
410 0 50.2 32.4 17.4 compounds, ketone compounds, phenolic compounds, and alcoholic
60 61.3 23.7 15.0 compounds. As the rubber additive, stearic acid is identified as the
460 0 52.0 30.2 17.8 dominant O-containing compound. Throughout the studied temperature
60 65.6 19.2 15.2
ranges, the content of N-compounds is > 10%. The rubber antioxidant

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L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

Table 4
Results of the ultimate analysis of the oils.
Condition Temperature Time (min) Ultimate analysis (wt%, dry)
(◦ C)
C H O N S H/C

Pyrolysis 320 0 85.3 11.0 2.1 0.4 1.2 1.54

360 0 86.2 11.3 1.2 0.5 1.3 1.61
410 0 86.6 11.1 1.2 0.5 1.1 1.58
460 0 86.2 11.2 1.1 0.5 1.0 1.54
Hydrolysis 320 0 85.5 11.2 1.8 0.3 1.2 1.57
60 85.5 11.3 1.7 0.3 1.3 1.59
360 0 85.5 11.3 1.6 0.3 1.3 1.59
60 85.9 11.2 1.6 0.3 1.0 1.56
410 0 86.2 10.9 1.5 0.4 1.1 1.51
60 86.3 10.8 1.5 0.4 1.0 1.51
460 0 86.5 10.3 1.7 0.4 1.1 1.42
60 86.6 9.7 2.1 0.5 1.1 1.34

Table 5
Molecular weight of the oils.
Pyrolysis Hydrolysis
Time (min) 0 0 60
Temperature(◦ C) 320 360 410 460 320 360 410 460 320 360 410 460
Molecular Weight 928 845 832 654 1130 987 702 378 842 793 746 593

Table 6
Results of the GC–MS analysis of the oils (area.%).
Condition Temperature Time (min) Aliphatic Aromatic O-compounds N,O-compounds S,N,O-compounds
(◦ C) (D-limonene)

Pyrolysis 320 0 33.75 (21.59) 36.92 13.85 11.71 3.78

360 0 50.51 (22.48) 19.90 13.32 14.38 1.89
410 0 51.01 (18.70) 22.24 13.50 12.11 1.14
460 0 36.88 (8.33) 28.47 12.60 16.12 5.94
Hydrolysis 320 0 27.97 (14.89) 8.87 31.89 28.18 3.09
60 32.07 (8.33) 22.56 12.93 30.10 2.33
360 0 53.75 (45.58) 22.75 10.85 12.65 0.00
60 37.13 (8.87) 42.54 14.77 5.56 0.00
410 0 24.67 (7.11) 59.05 9.90 6.04 0.35
60 18.90 (3.21) 65.71 8.86 6.01 0.52
460 0 7.11 (2.85) 76.68 8.69 5.75 1.77
60 14.53 (1.16) 72.04 4.97 7.13 1.32

N-(1,3-Dimethylbutyl)-N’-phenyl-p-phenylenediamine (6PPD) and 3.3.4. Analysis of the heavier fraction of oils

quinoline derivatives are the main N-compounds, along with a small The GC–MS is capable of analyzing the lighter fraction of chemical
amount of amides. The S,N-containing compounds such as benzothia­ compounds with a molecular weight of up to around 300 u [43]. As a
zole, O,N-containing compounds such as N,N-dibutyl-4-nitroaniline, and supplement to GC–MS, FTICR–MS is a powerful tool for examining the
O,S,N-containing compounds such as 2-(2-benzothiazolylthio)− 1-(3, heavier fraction of oils. A detailed knowledge of the chemical structure
5-dimethylpyrazolyl)-ethanone are also detected in oils, categorized as of hetero-compounds is fundamental to further refine the oils. The APPI
S,N,O-compounds herein. can effectively ionize aromatic compounds with weak polarity, while
In comparison with the pyrolysis process, the composition of oil ESI can analyze strong polar compounds [44]. Negative ESI mode can be
varies markedly with the increase in temperature during the hydrolysis used for determining neutral pyrrolic nitrogen and acidic compounds
process. At 320 ◦ C, the highest yields of O-compounds, N-compounds such as carboxylic acids and phenols [45]. Therefore, the combination of
and S,N,O-compounds are obtained, as the steam atmosphere facilitates positive APPI and negative ESI modes is conducive to understanding
the decomposition and release of additives from the tire at lower tem­ heteroatom compounds. The relative abundance of different class spe­
peratures. As the temperature increases to 360 ◦ C, the content of the cies is shown in Fig. 3. The ESI mode shows the existence of a large
aliphatic compounds drastically increases to 53.75%, primarily driven amount of heteroatom compounds and a minor amount of hydrocarbons
by a substantial amount of D-limonene (45.58%). At high temperatures, (HC), constituting less than 3%. Comparatively, the APPI mode indicates
the content of the aliphatic compounds drastically decreases at the a significant abundance of HC.
expense of the aromatic compounds, possibly due to the conversion of To understand the composition of the HC compounds, the relation­
alkenes like D-limonene into aromatics through cyclization and dehy­ ship among the carbon number, H/C, and DBE for the oils derived from
drogenation reactions [42]. At 460 ◦ C, the aromatic compound content the hydrolysis process was assessed using the APPI mode, and the cor­
peaks at 76.68%. The O-compounds experience a drastic reduction with responding results are shown in Fig. 4. At different temperatures, the
increasing temperature, decreasing to 4.97% at 460 ◦ C. At 360 ◦ C and carbon number predominantly falls within the range of 25 to 45, cor­
above, the contents of the N,O-compounds and S,N,O-compounds are responding to the boiling point of ~520 ◦ C [43]. The relative contents of
lower than those obtained from the pyrolysis process. the compounds with different carbon numbers are also compared. In the
hydrolysis process, the compounds with a carbon number of around 35
dominate at low-temperature ranges. At 460 ◦ C, the peak shifts to a

6
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

Fig. 3. Distributions of different compounds in the oils obtained at different temperatures; the processes were conducted for 60 min (a) ESI and (b) APPI. PY:
Pyrolysis; HY: Hydrolysis.

lower carbon number of around 31, aligning with the low molecular N6O4 accounts for ~45% at 320 ◦ C. Moreover, the oil at 320 ◦ C shows a
weight of the oils revealed by GPC. Under different conditions, the DBE wide DBE distribution ranging from 5 to 28. As the temperature in­
number above 6 can be observed for all the oils. This indicates that the creases to 360 ◦ C and above, the DBE shrinks into the range of ~5–15.
hydrocarbons in the heavier fraction of oils mainly exist in the form of Simultaneously, the percentage of the N6O2 subset is gradually
poly-aromatics, likely associated with the existence of styr­ increased to above 80% as the hydrolysis temperature increases to
ene–butadiene rubber and the cyclization of olefinic structures [46]. 460 ◦ C, possibly owing to the accelerated dehydration reaction [47].
Higher temperatures can increase the upper limit value of DBE. At The distributions of the NxOySz class compounds in the oils derived
320 ◦ C, the DBE is mainly located in the range between 6 and 12. With from the pyrolysis and hydrolysis processes are displayed in Fig. 7.
an increase in temperature to 460 ◦ C, the fraction of the oils with DBE Evidently, the N6OySz subset is dominant, accounting for more than
> 12 markedly increases to 50%, suggesting the formation of more 50%. A small fraction of N7OySz and N8OySz can also be observed.
fused-ring aromatics at high hydrolysis temperatures. This result is Similar to the HC and N6Ox classes, the composition of the NxOySz class
consistent with the low H/C ratio of the oils formed at high hydrolysis only varies slightly with changes in the pyrolysis temperatures. Simi­
temperatures as shown in Table 4. larly, N6OxSy, N7O1S1, and N8O1S1 are the most abundant subsets in
The relationship among the carbon number, H/C, and DBE of the oils the oils derived from the hydrolysis process. In contrast to the pyrolysis
produced during the pyrolysis process is depicted in Fig. 4. Similar to the process, more subsets can be observed in the oils derived from the hy­
oils derived from the hydrolysis process, most compounds are identified drolysis process at 320 ◦ C. This result indicates that the hydrolysis
in the carbon number range between 25 and 45. The compounds with 35 process can effectively extract hetero-compounds at this temperature. As
carbon atoms show the highest content. For all four oils, the DBE is the hydrolysis temperature increases, parts of the subset are eliminated,
larger than 6, indicating the dominance of aromatics. Similar to the indicating the decomposition of the extracted hetero-compounds.
hydrolysis process, the upper limit value of DBE is markedly increased to For the NxSy class, only the NxS1 subset is detected. Therefore, the
around 17 as the temperature increases to 360 ◦ C. However, the upper relationship between the carbon number and DBE for the NxS1 subset is
limit value of DBE for pyrolytic oils produced at 460 ◦ C is much lower summarized in Fig. 8. For the pyrolytic oils, the carbon number is
than those from the hydrolysis process, indicating that the hydrolysis stretched from around 10 to 40, and the DBE of most compounds is
process is beneficial for the dehydrogenation reaction. larger than 4, indicating the dominance of N,S-containing aromatic
As illustrated in Fig. 3, the ESI mode can detect large amounts of compounds. Under all the conditions, the N3S1 and N6S1 subsets ac­
heteroatom compounds, including Nx, Ox, NxOy, NxOySz, NxSy, and count for more than 80%, and the distribution of the different subsets is
OxSy classes. These heteroatom compounds are derived from the barely affected by the pyrolysis temperatures. For the hydrolysis pro­
decomposition of different types of additives incorporated during tire cess, a large number of NxS1 compounds can be observed at 320 ◦ C. As
manufacturing. The NxOy class is the most abundant in the oils and is the temperature increases, the number of compounds decreases. Only
possibly formed by the reaction between the rubber antioxidants and the N6S1 and N7S1 subsets are observed for the oils obtained at 360 ◦ C
stearic acid [47]. Therefore, the NxOy class is further classified in Fig. 5. and above.
Evidently, the pyrolysis temperature has a minor effect on the distri­ The relationship between the carbon number and DBE for different
bution of the NxOy subsets, while high hydrolysis temperatures can Nx subsets is illustrated in Fig. 9. Evidently, the number of compounds
promote the formation of N5Ox at the expense of N6Ox. Among the increases markedly as the pyrolysis temperature increases from 320 to
different NxOy subsets, the N6Ox subset is dominant, accounting for 460 ◦ C. This result indicates that a high pyrolysis temperature can
more than 70%. Therefore, the subset of N6Ox is further classified based promote the formation of N-containing compounds, consistent with the
on the oxygen number in Fig. 6. For pyrolytic oils, the carbon number is results of the ultimate analyses, which reveal the presence of high ni­
mainly located in the range between 8 and 40, and the oxygen number is trogen concentrations in the oils (Table 4). The N4 subset is the most
higher than 6. The percentage of N6O2 is more than 65% for all the oils, abundant compound, followed by the N7 subset. Under all the pyrolysis
followed by N6O3 and N6O4. The DBE of the different oils derived from conditions, the carbon number of oils is distributed in the range of
the pyrolysis process is mainly located in the range between 5 and 15, 20–40. The DBE is located in the range between 6 and 14 at 360 ◦ C, and
indicating the dominance of hetero-aromatic compounds. These results the upper limit value increases to 20 as the temperature increases to
indicate that the effect of the pyrolysis temperature on the composition 460 ◦ C. This result indicates the existence of nitrogen cyclic aromatic
of the N6Ox subset is weak. For the hydrolysis process, the subset of compounds in the heavy fraction of oils as well as confirms the

7
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

Fig. 4. APPI-analyzed relationship among carbon number, H/C, and DBE for the oils. Pyrolysis: (a) 320 ◦ C, (b) 360 ◦ C, (c) 410 ◦ C, and (d) 460 ◦ C; Hydrolysis: (e)
320 ◦ C, (f) 360 ◦ C, (g) 410 ◦ C, and (h) 460 ◦ C.

8
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

nitrogen in oils remains in the range between 24 and 30 wt%. At 320 ◦ C,

more than 50 wt% nitrogen is already transferred into the gas phase.
Similar to oxygen, increasing reaction time can promote the release of
nitrogen from char into gas, while the fraction of nitrogen in oil remains
almost constant.
Unlike oxygen and nitrogen, the sulfur in the tire is nearly
completely converted at 320 ◦ C, resulting in more than 60 wt% of sulfur
in char owing to the formation of ZnS [37]. At low temperatures of 320
and 360 ◦ C, around 30 wt% sulfur is transferred into the liquid phase for
both pyrolysis and hydrolysis. As the temperature increases to 410 ◦ C,
the sulfur content in the oil drastically decreases, indicating the
decomposition of condensable S-containing compounds into
sulfur-containing gases. Increasing the reaction time can promote the
release of sulfur in the char and oil phases into the gas phase, especially
at temperatures above 410 ◦ C.

4. Discussion

For both hydrolysis and pyrolysis of tire, the formation of oil is

Fig. 5. ESI results of the subset of NxOy compounds in the oils. PY: Pyrolysis;
dependent on the process temperature. Tire degradation at different
HY: Hydrolysis.
temperatures involves (1) decomposition of additives; (2) decomposi­
tion of rubber; (3) cracking of primary product; and (4) recombination
promotion of dehydrogenation at high pyrolysis temperatures. An of primary product. The decomposition of additives leads to the for­
opposite trend is evident for the hydrolysis process. At 320 ◦ C, more mation of various hetero-containing compounds, while rubber decom­
compounds with wide DBE and carbon number distributions are position yields valuable aromatics or aliphatics. The formed primary
observed in the oils derived from the hydrolysis process. At 360 ◦ C and product, including hetero-containing compounds, aliphatics, and aro­
above, the number of N-containing compounds observed is low, indi­ matics, may experience different extents of cracking and recombination
cating that parts of the N-containing compounds undergo reactions. The cracking of the primary product yields low-weight oils,
decomposition. while the recombination reaction forms heavy oils. These reactions are
The relationship between the carbon number and DBE for the O- temperature and residence times-dependent. As the temperature in­
containing compounds is shown in Fig. 10. The carbon number ranges creases, sufficient energy is supplied into the reaction system, allowing
from 16 to 28 for the oils derived from the pyrolysis process, and the the breaking of the strong polymer bonds [48]; as a result, severe
largest number of compounds is observed in the range of 16–19. For the decomposition of rubber into volatiles is observed. Therefore, the oil
pyrolysis process, the amounts of the O2 and O4 subset compounds yield decreases with increasing hydrolysis and pyrolysis temperatures.
account for more than 60% and 20%, respectively. The O2 subset with In this study, the sample was heated in a closed vessel. The formed
one DBE is possibly derived from the stearic acid derivatives, while the volatiles may experience various extents of secondary cracking re­
O4 subset with two DBE indicates the existence of esters. Unlike the actions, leading to the formation of a large amount of gas. Especially, the
pyrolysis process, the carbon number of the oils derived from the hy­ slow ramping and cooling periods shown in Figure SM-2 may accelerate
drolysis process is located in the range between 16 and 34. Moreover, the secondary reaction in the closed space. Therefore, a decrease in the
large amounts of compounds containing 32 carbon atoms, 4 oxygen oil content is observed at high temperatures. Contrarily, the tire mainly
atoms, and 1 DBE can also be formed by the recombination reaction of undergoes liquefaction at 320 ◦ C during the hydrolysis process. With the
stearic acid. At 460 ◦ C, the content of the O2 subset compounds can assistance of steam, most additives and parts of rubber can be more
reach up to ~55%. easily extracted from the tire due to the higher ionic product of water
and lower dielectric constant of steam [49]. As a result, most
3.4. Heteroatom balance hetero-containing compounds with a higher polarity are formed at
320 ◦ C. At high hydrolysis temperatures, the decomposition of rubber
The element partition of oxygen, nitrogen, and sulfur among the dominates, leading to the maximum yield of D-limonene at 360 ◦ C.
three-phase products is shown in Fig. 11. In both the pyrolysis and hy­ Simultaneously, the cracking reaction accelerates, resulting in the pro­
drolysis processes, high temperatures can promote the transfer of oxy­ duction of low-weight oils. At 410 ◦ C, the cracking reaction surpasses
gen from the oil and solid phases to the gas phase. At 320 ◦ C, the oxygen the decomposition of rubber. At this stage, the recombination reaction of
content in the oil from the pyrolysis process is high (16.5 wt%) and the free radicals does not dominate owing to the “cage effect” of the
comparable to that of the oil (16.4 wt%) produced from the hydrolysis water atmosphere [19]. As the temperature increases to 460 ◦ C, the
process. As the temperature increases to 360 ◦ C, the oxygen contents in balance is gradually shifted from the cracking reaction to recombination
the oil and char drastically decrease to 9.2 and 22.7 wt%, respectively, and dehydrogenation reactions. This can be evidenced by the production
due to decomposition. In comparison, the oxygen fraction in the oils of high-molecular-weight oils with low H/C ratios at extended reaction
derived from hydrolysis is higher than that derived from the pyrolysis times. Therefore, we can conclude that the hydrolysis of tires experi­
process at 360 ◦ C and above. As the hydrolysis reaction proceeds, more ences the extraction of additives, decomposition of rubber, cracking of
oxygen is transferred from the solid phase to the gas phase, while the primary product, and recombination reactions following a stepwise re­
oxygen content in the oil is only slightly reduced. These results action procedure.
demonstrate that the pyrolysis process can promote deoxygenation of Comparatively, elemental analysis and composition of oils show
oils with the assistance of char. minimal variation with increasing pyrolysis temperatures. Moreover,
During the pyrolysis process, nitrogen is nearly completely trans­ the MWs of pyrolytic oils are much greater than those of oils from the
formed into liquid and solid phases at 320 ◦ C. As the pyrolysis temper­ hydrolysis process. In the pyrolysis process, once the oil is formed, it can
ature increases, more nitrogen is transferred into the gas phase. Unlike undergo a secondary reaction involving cracking and recombination
the pyrolysis process, the effect of temperature on nitrogen migration is reactions under the N2 atmosphere. The cracking reaction can be
negligible for the hydrolysis process. At all hydrolysis conditions, the accelerated with the assistance of char, leading to the formation of more

9
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

Fig. 6. ESI results of the subset of N6Ox compounds in the oils produced from pyrolysis and hydrolysis. Pyrolysis: (a) 320 ◦ C, (b) 360 ◦ C, (c) 410 ◦ C, and (d) 460 ◦ C;
Hydrolysis: (e) 320 ◦ C, (f) 360 ◦ C, (g) 410 ◦ C, and (h) 460 ◦ C.

10
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

Fig. 7. ESI results of the subset of NxOySz compounds in the oils produced from pyrolysis and hydrolysis. Pyrolysis: (a) 320 ◦ C, (b) 360 ◦ C, (c) 410 ◦ C, and (d)
460 ◦ C; Hydrolysis: (e) 320 ◦ C, (f) 360 ◦ C, (g) 410 ◦ C, and (h) 460 ◦ C.

11
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

Fig. 8. ESI results of the subset of NxS1 compounds in the oils produced from pyrolysis and hydrolysis. Pyrolysis: (a) 320 ◦ C, (b) 360 ◦ C, (c) 410 ◦ C, and (d) 460 ◦ C;
Hydrolysis: (e) 320 ◦ C, (f) 360 ◦ C, (g) 410 ◦ C, and (h) 460 ◦ C.

12
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

Fig. 9. ESI results of the subset of Nx compounds in the oils produced from pyrolysis and hydrolysis. Pyrolysis: (a) 320 ◦ C, (b) 360 ◦ C, (c) 410 ◦ C, and (d) 460 ◦ C;
Hydrolysis: (e) 320 ◦ C, (f) 360 ◦ C, (g) 410 ◦ C, and (h) 460 ◦ C.

13
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

Fig. 10. ESI results of the subset of Ox compounds in the oils produced from pyrolysis and hydrolysis. Pyrolysis: (a) 320 ◦ C, (b) 360 ◦ C, (c) 410 ◦ C, and (d) 460 ◦ C;
Hydrolysis: (e) 320 ◦ C, (f) 360 ◦ C, (g) 410 ◦ C, and (h) 460 ◦ C.

14
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

Fig. 11. Carbon, hydrogen, sulfur, nitrogen, and oxygen balance. PY: Pyrolysis; HY: Hydrolysis.

gas at the expense of oils. Parts of the cracked product may undergo a reactor at various temperatures to demonstrate the decomposition
recombination reaction, forming a high-molecular-weight oil, unlike the behavior of tires under different atmospheres; especially, the behaviors
“cage effect” of the hydrolysis process. Therefore, in contrast to the of hetero-elements oxygen, nitrogen, and sulfur were examined. In both
hydrolysis process, the pyrolysis process can simultaneously promote pyrolysis and hydrolysis processes, high temperatures promoted the
cracking and recombination reactions. This simultaneous cracking/ cracking of the rubber macromolecules, resulting in the formation of
recombination of the primary product leads to the formation of heavy low-weight products. Thus, a maximum amount of the aliphatics, mainly
oils, making the pyrolysis process less sensitive to temperature change. D-limonene, was formed at 360 ◦ C and then converted to aromatics at
In the case of hetero-containing compounds, the hydrolysis process further higher temperatures owing to accelerated dehydrogenation re­
enables early release of hetero-elements. However, the oxygen content actions. The hydrolysis of tires enabled the extraction of additives,
in the corresponding oils is higher than that in the oils produced during decomposition of rubber, cracking of primary products, and recombi­
the pyrolysis process possibly owing to the involvement of water during nation reactions, following a stepwise reaction procedure. Due to the
the reaction. Conversely, the strong cracking reaction can promote “cage effect” of the water atmosphere, the cracking reaction was pro­
deoxygenation during the pyrolysis process as reflected by the low ox­ moted, while the recombination reaction was hindered. Therefore, the
ygen content in the corresponding oils as well as by the observed small hydrolysis process yielded low-molecular-weight oils, as evidenced by
number of Ox class compounds and a large number of Nx class com­ the significant formation of low-weight aromatics, which were detected
pounds in the heavy oils derived from the pyrolysis process. by GC–MS. In a 60-minute hydrolysis process at 460 ◦ C, high-molecular-
weight oils were produced, indicating a gradual shift from decomposi­
5. Conclusions tion to recombination as the reaction proceeded. Comparatively, the
pyrolysis temperature had a less pronounced effect on the oil formation
Pyrolysis and hydrolysis of the tire were conducted in an autoclave and char characteristics. Unlike the hydrolysis process, the pyrolysis

15
L. Wang et al. Journal of Hazardous Materials 468 (2024) 133724

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scrap tire to liquid fuel. Chem Eng J 285, 157–163.
the work reported in this paper.
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