Energy 262 (2023) 125519

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Energy
journal homepage: www.elsevier.com/locate/energy

Optimal production of waste tire pyrolysis oil and recovery of high

value-added D-limonene in a conical spouted bed reactor
Jae Gyu Hwang, Byeong Kyu Lee, Myung Kyu Choi, Hoon Chae Park, Hang Seok Choi *
Division of Environmental and Energy Engineering, Yonsei University, Yeonsedae-gil 1, Wonju-si, Republic of Korea

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

Keywords: Owing to the rapid increase in the global automobile demand, the disposal of waste tires has become a severe
Conical spouted bed reactor problem. Most waste tires are reclaimed and incinerated; exhaust gas and ash from incineration comprise
D-limonene harmful substances and dust. Therefore, in this study, fast pyrolysis technology was investigated to overcome the
Fast pyrolysis
limitations of traditional methods and stably treat waste tires. Fast pyrolysis experiments were performed in a
Pyrolysis oil
Waste tire
conical spouted bed reactor (CSBR) to investigate the optimal pyrolysis conditions for waste tires with respect to
the reaction parameters: reaction temperature, superficial gas velocity, and feeding rate. The characteristics of
waste tire pyrolysis oil (WTPO), which is the main target material for fast pyrolysis, were analyzed through
moisture, higher heating value (HHV), and viscosity. The optimal pyrolysis conditions were a reaction tem­
perature of 450 ◦ C, superficial gas velocity of 1.1, and feeding rate of 1 kg/h. Under these conditions, the WTPO
yield was 66.9 wt% and energy efficiency was 82.1%. Furthermore, to recover high value-added D-limonene, the
WTPO produced under optimal conditions was distilled, and gas chromatography mass spectrometry (GC-MS)
analysis was performed to evaluate the product. According to the distillation experiment, the recovery efficiency
of D-limonene was highest at 4 h.

waterways and estuaries, create leachate, and disrupt the surrounding

1. Introduction
Today, the use of alternative fuels is the most promising way to
reduce fossil fuel consumption and achieve net-zero. To this end, it is
important to select the appropriate technology to improve the efficiency
and economy of each alternative fuel [1,2]. Research and development
related to the treatment of anthropogenic wastes, such as waste tires,
waste plastics, and electronic waste, is being increasingly conducted
around the world. The amount of waste tires, a polymer waste material
mainly comprising natural and synthetic rubber, has been increasing
every year since the advent of the automobile era. As a result, waste tire
disposal has become a severe problem. Approximately 1.5 billion waste
tires are produced annually worldwide, approximately 20 million tons of
which are produced in major consumer countries such as the United
States, China, and Japan, and all throughout Europe [3]. Waste tires are
bulky and require considerable time for biodegradation; therefore, their
disposal in landfills is not appropriate. Waste tires illegally dumped and
buried in open storage yards in Southeast Asia cause diseases by
providing habitats for pests such as mosquitoes, block water flow in
ecosystem. In addition, dumped waste tires are a fire hazard, and when a
fire occurs, a large number of pollutants are emitted, which cause sec­
ondary environmental pollution and pose environmental risks for
humans, animals, and plants [4–7]. The recycling of waste tires is mainly
classified as material recycling, which involves recycling waste mate­
rials into other products by changing their shape, and thermal recycling,
which recovers the heat through combustion [8]. Specifically, material
recycling includes a method of reusing waste tires in their original form
for landfill construction and processing tires into powder and rope form
for application in playgrounds, building materials, or asphalt mixing.
Thermal recycling, also called energy recovery, is a method of recov­
ering the waste heat generated after the combustion of waste tires and
using it as an energy source. However, these waste tire recycling
methods are not eco-friendly, as they generate harmful substances.
Material recycling can causes soil pollution because of the leaching of
polyaromatic hydrocarbons (PAHs) and heavy metals, such as lead, that
are present in waste tires [9]. Regarding thermal recycling, substantial
amounts of harmful substances, such as sulfur oxides (SOx), PAHs, and
dioxins, generated during the combustion process are emitted, causing

Abbreviations: CSBR, conical spouted bed reactor; WTPO, waste tire pyrolysis oi; CB, carbon black; NGC, non-condensable gas; HHV, higher heating value; TGA,
thermogravimetric analysis.
* Corresponding author.
E-mail address: hs.choi@yonsei.ac.kr (H.S. Choi).

https://doi.org/10.1016/j.energy.2022.125519
Received 5 July 2022; Received in revised form 2 September 2022; Accepted 19 September 2022
Available online 22 September 2022
0360-5442/© 2022 Elsevier Ltd. All rights reserved.
J.G. Hwang et al. Energy 262 (2023) 125519

terpenoid alcohol, and drinks [35]. D-limonene is a safe terpene hy­

Nomenclature drocarbon and is mainly extracted from lemon and orange peels. It is
mostly produced in Florida, USA, where orange production is high.
dp Particle diameter (m) However, since lemon and orange peels occur intensively for a short
D Column diameter (m) period of 2–3 months, the supply stable of raw materials is difficult for
Di Fluid-inlet diameter (m) D-limonene production [36]. To solve this problem, studies have been
g Acceleration due to gravity (m/s2) conducted to recover D-limonene from WTPO. Islam et al. [37] obtained
H Bed depth (m) highest WTPO yield of 55 wt% at the 475 ◦ C and confirmed that limo­
ρp Absolute density of particle (kg/m3) nene occupied the largest peak area among the components of WTPO
ρ Fluid density (kg/m3) from GC-MS. Also, few studies were conducted using other feedstocks,
but the amount of D-limonene contained was smaller than that of WTPO
[38–40]. Besides there have been studies on the production of WTPO,
but few studies have been conducted on the separation of D-limonene
air pollution that has a considerable impact on humans and the envi­ from WTPO. Some researchers studied the influence of the fast pyrolysis
ronment [10]. Therefore, there is an emerging need for the development conditions to obtain the maximum yield of D-limonene, but most were
of technology to convert waste tires into energy more stably and limited to the change of reaction temperature [41–43]. Therefore, it is
economically. strongly needed to study the influence of various fast pyrolysis condi­
Among waste tire energy conversion methods, fast pyrolysis is a tions on the yield of D-limonene. Hence, in this study, the optimal fast
technology for thermally decomposing waste tires at temperature of pyrolysis conditions for producing high-quality WTPO using a CSBR
400–600 ◦ C under anoxic conditions [11]. Unlike combustion, it is were derived. Furthermore, the D-limonene yield in WTPO was analyzed
attracting attention as an eco-friendly process that generates fewer with respect to several fast pyrolysis conditions such as reaction tem­
pollutants, such as harmful gases and dust. Accordingly, multiple studies perature, superficial gas velocity, and feeding rate. A study was also
have been conducted on the fast pyrolysis of waste tires, which can be conducted on the optimal recovery of D-limonene from WTPO through
largely divided into research on the pyrolysis of waste tires and research fractional vacuum distillation.
on the recovery of high value-added materials from WTPO. Experi­
mental studies have been conducted to derive the optimal conditions for 2. Materials and methods
waste tire pyrolysis depending on the main operating parameters, such
as the reactor type, raw material composition, reaction temperature, 2.1. Experimental materials
pressure, sample particle size, temperature increase rate, flow rate of
input gas, and gas residence time [12–21]. Additionally, as the main In this study, a Korean waste tire recycling company provided waste
purpose of fast pyrolysis is to produce and utilize high-quality pyrolysis tire scrap for fast pyrolysis and D-limonene recovery. The waste pas­
oil, studies on the characteristics of WTPO, produced under various senger car tire scrap was obtained by removing the iron core after
process conditions, have also been conducted [22–26]. The CSBR is a crushing. To analyze the physical and chemical properties of the waste
type of fluidized bed reactor and has been used in various processes tire sample, waste tire scrap with a size of 1–2 mm was extracted
since it was first designed by Mathur and Gishler [27]. The CSBR facil­ through ASTM Sieve 10 and 18. Table 1 shows the physical and chemical
itates contact between solids and gases through the formation of an properties of the waste tire and other waste resources. The waste tire
annulus around the jet after injecting the fluid in the vertical direction to consisted of 67.58 wt% volatile and 25.16 wt% fixed carbon, with a
the center of the solid layer below the reactor, and spraying it in the form moisture content less than 1 wt% and ash content of 6.61 wt%. In the
of a jet. Owing to these characteristics, the CSBR has excellent heat and elemental analysis, the carbon content was the highest at 82.85 wt%,
mass transfer rates and can be applied to irregular and highly sticky and the hydrogen, oxygen, nitrogen, and sulfur contents were 7.64 wt%,
samples, thereby reducing the energy required for particle pulverization 7.06 wt%, 0.39 wt%, and 1.97 wt%, respectively. The HHV of the scrap
[28]. Additionally, as an internal gas distribution plate is not required, was 35.69 MJ/kg. The physicochemical analysis of waste resources
the pressure drop is lower than that of a fluidized bed, and scale-up is showed that waste tires are suitable for recovering high-quality pyrol­
easy because of its uncomplicated design [29]. Arabiourrutia et al. py­ ysis oil compared with other waste resources owing to their low mois­
rolyzed 1 mm pieces of a scrap tire using a CSBR at 425–610 ◦ C, under a ture content and high volatile matter content. In contrast, owing to the
nitrogen atmosphere, and derived the reaction kinetics. The results high content of ash and sulfur, an appropriate purification process may
confirmed that the performance of the model, considering the secondary be required [44–46].
reaction, was slightly better than that considering the simple reaction Thermogravimetric analysis (TGA) was performed to investigate the
[30]. Lopez et al. pyrolyzed waste tires using a CSBR at a reaction thermal degradation characteristics of the waste tire. An analyzer
temperature of 425–600 ◦ C and recovered up to 55.0 wt% of WTPO. In
addition, it has been confirmed that a CSBR is suitable for the thermal
Table 1
decomposition of waste tires because it can continuously remove carbon
Physical and chemical properties of waste tire and other waste resources [47,
black (CB) [31]. Alvarez et al. evaluated the quality of WTPO produced 48].
through CSBR. The study indicated that the calorific value of WTPO
Physical Waste Solid refuse Polyethylene Sawdust
increased as the reaction temperature increased, and WTPO was judged
properties tire fuel (SRF) (PE) [48] (larch) [47]
to have the potential to replace fossil fuels. However, it was noted that
treatment with sulfur, nitrogen, and aromatics is necessary [32]. This is Moisture Content 0.65 9.98 0 11.24
(wt.%)
because these substances in WTPO impede utilization as a fuel. Mean­ Volatile (wt.%) 67.59 59.37 98.57 67.49
while, WTPO has high value-added components such as D-limonene and Fixed carbon 25.16 5.84 0.03 19.76
benzene, toluene, and xylene (BTX). These are important factors for (wt.%)
WTPO to have economic competitiveness with other fuels [33]. Limo­ Ash (wt.%) 6.61 24.81 1.4 1.51
Element C 82.93 49.01 84.35 51.28
nene is the main ingredient of citrus oil (over 80%) and exists in two
(wt.%) H 7.64 7.11 15.64 6.17
forms: D-limonene and dl-limonene [34]. D-limonene is applicable to a O 7.06 43.29 0 42.19
wide range of industries such as formulation of eco-friendly cleaner, N 0.39 0.59 0.01 0.36
industrial solvents, resins, adhesives, and dispersing agent for pigment. S 1.97 0 0 0
In addition, it is often used as a feedstock for fragrance of toothpaste, HHV (MJ/kg) 35.69 19.51 45.51 19.24

2
J.G. Hwang et al.
(LECO, TGA701) was used for the TGA analysis, which was performed in
accordance with ASTM E 1131. The weight loss of the waste tire per unit
of time was measured at a temperature range from 25 to 800 ◦ C, at
10 ◦ C/min. A 1 g sample was used for TGA, and measurements were
performed in an oxygen-free atmosphere, using nitrogen as the carrier
gas. Fig. 1 shows the thermogravimetric analysis of the waste tire. It was
confirmed that the thermal degradation of waste tires proceeds in three
stages. The first stage occurs at 200–350 ◦ C. In this stage, the moisture,
oil, plasticizers, and various additives used in the tire manufacturing
process evaporate. The second and third stages appeared at 330–420 ◦ C
and 430–500 ◦ C, respectively. In the second stage, weight loss primarily
occurs because of the decomposition of natural rubber (NR) [49]. In the
third stage, weight loss likely occurs because of the decomposition of
synthetic rubbers, such as butadiene rubber (BR) and styrene-butadiene
rubber (SBR) [50,51]. The waste tire used in the present study showed
the greatest weight loss in the second stage; therefore, it had a greater
NR than BR or SBR. Additionally, a reaction temperature from 400 to
550 ◦ C was necessary for the waste tire to be sufficiently thermally
decomposed.
Fig. 2 shows the WTPO and distillation oil obtained after the fast
pyrolysis and distillation processes. WTPO, a liquid product of fast py­
rolysis, has comparable properties to commercial light crude oil and
heavy crude oil, with a higher calorific value than that of coal. In
addition, WTPO is composed of various organic compounds, including
aromatic compounds, and contains high value-added hydrocarbons,
such as benzene, toluene, xylene, and limonene. As the D-limonene
present in WTPO has the same chemical formula (C10H16) as natural D-
limonene extracted from lemon or orange peel, D-limonene recovered
from WTPO could be used as a raw chemical material [52]. D-limonene,
which is typically extracted from lemon or orange peel, is a terpene
hydrocarbon and a biodegradable natural substance with excellent sol­
ubility in fatty acids and mineral oil. Because of its refreshing scent and
non-toxicity to the human body, D-limonene is used in perfumes, air
fresheners, soaps, and food. D-limonene, widely used throughout the
industry as an eco-friendly cleaner, is mostly produced in Florida, USA,
where orange production is high. However, a stable supply of natural
D-limonene is difficult to obtain owing to the limited production time.
To resolve this problem, D-limonene could recovered from WTPO [53].
2.2. Experimental apparatus and method
In this study, waste tire fast pyrolysis was performed using a CSBR.
Fig. 3 shows a schematic of the fast pyrolysis apparatus. The waste tire
fast pyrolysis system consisted of the sample feeding part, the reaction
part, where the pyrolysis reaction of waste tire occurs, and the pyrolysis
Fig. 1. Thermogravimetric analysis of waste tire.
3
Energy 262 (2023) 125519
Fig. 2. Photograph of WTPO (left) and distillation oil (right).
oil recovery part, which condenses vapors into a liquid and collects oil
mist using a condenser and electrostatic precipitator (EP). More spe­
cifically, the pyrolysis system comprised a sample silo, two screw
feeders, a spouted bed reactor, cyclones, condensers, an EP, and I/D
(Induced draft) fans. The waste tire was fed into the reactor via a two-
stage screw feeder. The sample was placed in the screw feeder at the
top, and the bottom screw feeder was used to quickly feed the sample
into the reactor. The CSBR was used for fast pyrolysis with a height of
500 mm, reactor diameter of 159 mm, cone bottom diameter of 50 mm,
gas inlet diameter of 25 mm, and cone angle of 44◦ . The reactor was
made of SUS 304 to withstand elevated temperatures and oxidation
conditions. The reactor was then placed in an electric furnace. Nitrogen
gas was used for bed fluidization. In an anaerobic atmosphere, the waste
tire was heated and decomposed into volatiles, CB, and non-condensable
gas (NCG). The gas mixture and CB particles were emitted into the cy­
clones. While passing through the two cyclones, larger and heavier
particles were collected in the first cyclone and lighter and smaller
particles were collected in the second cyclone. Subsequently, the clean
gas mixture entered the shell and tube condenser to condense the vol­
atiles into pyrolysis oil. Fine oil mist that could not be recovered from
the condenser was collected through an EP. Pyrolysis oil was collected in
bottles at the bottom of the condenser and EP. To prevent a pressure
increase in the pyrolysis system, an I/D fan was installed at the end of
the process. The NCG was discharged into the atmosphere through the I/
D Fan. The main objective of the waste tire fast pyrolysis process was to
recover high-quality WTPO. Reaction parameters such as the reaction
temperature, heating rate, particle size, composition, carrier gas flow
rate, and gas residence time can directly affect the quality of WTPO [54].
Considering this, the experimental conditions for fast pyrolysis were set
as shown in Table 2, and the optimal conditions were derived by
adjusting the parameters. The reaction temperature was changed from
400 to 550 ◦ C with reference to TGA, and the experiment was performed
by changing the feeding rate and superficial gas velocity in a range of
0.5–1.5 kg/h and 0.8–1.4, respectively. Silica sand (Joomoonjin Co.,
Ltd.) was used as the bed material, with a mean particle diameter of 466
mm, which belongs to the Geldart B classification.
The distillation apparatus shown in Fig. 4 was manufactured after
preliminary experiments, the conditions of which are listed in Table 3.
The apparatus consisted of a distillation flask, fractionation column,
condenser, and a vacuum pump. To apply the vacuum distillation
method, the internal pressure was set to 60 mm Hg through 700 mm Hg
decompression with a vacuum pump. The temperature of the distillation
flask was controlled using a heating mantle. Unlike simple distillation,
the vapor in this recovery device is liquefied and re-gasified through a
fractionation column and a Dimroth condenser and circulated inside the
column. During this process, the purity of the vapor can be increased,
J.G. Hwang et al. Energy 262 (2023) 125519

Fig. 3. Schematic diagram of fast pyrolysis apparatus.

Table 2
Experimental conditions for waste tire fast pyrolysis.
Conditions Value

Reaction temperature (◦ C) 400–550

Superficial gas velocity (U/Ums) 0.8, 1.1, 1.4
Feeding rate (kg/h) 0.5, 1.0, 1.5
Sample particle size (mm) 1–2
Bed particle mean diameter (mm) 466 (Geldart B)

allowing the extraction of high-purity D-limonene using a Liebig

condenser. The synthesis gas that was not captured by the condensers
was evacuated to a vacuum pump through a cold trap.

3. Results and discussion

This section outlines the yield of the pyrolysis products and the
characteristics of WTPO with respect to the experimental parameters.
Before fast pyrolysis, a pressure drop experiment was performed ac­
cording to the superficial gas velocity. The minimum spouting velocity
(Ums) was derived by analyzing the pressure drop and root mean square
(RMS), based on which the operating conditions of the CSBR were set.
Fast pyrolysis of waste tire scrap was conducted using different reaction
temperatures, superficial gas velocities, and feeding rates, as they have a
major influence on the results of fast pyrolysis. Thereafter, the D-limo­
nene in WTPO was recovered through a distillation experiment, and the
recovery efficiency of D-limonene was evaluated through GC-MS
analysis.

3.1. Hydrodynamic characteristics of CSBR Fig. 4. Schematic diagram of D-limonene recovery apparatus.

CSBRs have the advantages of excellent heat and mass transfer rates, the operation regime, and operate it in the spouting regime. An acrylic
a low pressure drop in the reactor, and applicability for nonhomoge­ cold bed test apparatus was fabricated to investigate the hydrodynamic
neous samples [55,56]. Therefore, it is particularly important to un­ characteristics of the CSBR. The pressure drop and RMS values of the
derstand the hydrodynamic characteristics of the CSBR, accurately set

4
J.G. Hwang et al. Energy 262 (2023) 125519

Table 3
Experimental conditions for D-limonene recovery distillation.
Conditions Value

Distillation time (h) 1, 2, 4, 8

Vapor pressure (mmHg) 60
Boiling temperature (◦ C) 96

pressure fluctuations in the CSBR with respect to the superficial gas

velocity change were measured, as shown in Fig. 5. The pressure drop in
the CSBR gradually increased as the superficial gas velocity increased,
reaching a maximum of 2978 Pa at a superficial gas velocity of 2.71 m/s
(point A). Thereafter, the pressure drop gradually decreased as the su­
perficial speed increased, and the pressure drop remained constant after
5.09 m/s. The minimum fluidization velocity (Umf) of a fluidized bed is
defined as the initial inflection point at which the pressure after the
fixed-bed regime remains constant in the pressure drop diagram [57].
However, there is a limitation in deriving the Ums using only the pressure
drop in a CSBR because the pressure decreases after the maximum
pressure drop point and then remains constant. Therefore, Ums was Fig. 6. Yield of pyrolysis products with respect to reaction temperature [58].
derived by considering the RMS of the pressure fluctuation, together
with the pressure drop. In the CSBR, the superficial gas velocity is the
lowest at the top of the bed, and when the particles start to fluidize at the
top, all particles in the bed are fluidized, and this velocity can be defined
as Ums. The RMS value increased linearly owing to the vibration of
particles in the CSBR before point A, which represents the fixed-bed
regime, and increased significantly at point A, where the pressure
drop was at its maximum. Subsequently, the RMS value showed the
largest slope at point B, where particles in the CSBR started to spout. As
the particles in the CSBR spouted, the pressure drop gradually
decreased, the RMS value increased, and the slope of the RMS value
changed after point C. At this point, it was predicted that the flow regime
would transition from a stable spouting regime to a dilute-phase
spouting regime. As a result of the cold bed test, the Ums at point B
was selected, where the slope of the RMS value is largest, and the su­
perficial gas velocity is 3.4 m/s. Ums was calculated using Equation (1).
( / ) √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
( )/
Ums = dp D (Di /D)1/3 2gH ρp − ρ ρ (1) Fig. 7. Water content, viscosity, and HHV of WTPO with respect to reaction
temperature.

3.2. Characteristics of WTPO with respect to reaction temperature

Figs. 6–8 show the characteristics of WTPO with respect to the re­
action temperature. The reaction temperature has the greatest influence
on the fast pyrolysis process. This effect was investigated by changing
the reaction temperature from 400 to 550 ◦ C. Fig. 6 shows the yields of
WTPO, CB, and NCG with respect to the reaction temperature. The
experimental results were compared to simulated results of Olazar et al.

Fig. 8. Energy efficiency of WTPO with respect to reaction temperature.

[58]. When the reaction temperature was increased from 400 to 450 ◦ C,
the yield of WTPO increased from 43.4 wt% to 67.0 wt%., and on
increasing the temperature further to 550 ◦ C, the yield decreased to
35.8 wt%. In the TGA of the waste tire (Fig. 1), approximately 15 wt% of
Fig. 5. Pressure drop and RMS with respect to superficial gas velocity.

5
J.G. Hwang et al. Energy 262 (2023) 125519

weight loss occurs after the 3rd decomposition stage (500 ◦ C). There­
fore, it can be predicted that the WTPO yield will increase as the reaction
temperature increases; however, in the actual fast pyrolysis experiment,
the yield of WTPO decreased after 450 ◦ C. This is because the secondary
reaction of tar occurs as the pyrolysis temperature increases, and tar
decomposes into CB or NCG [59–61]. The CB content decreased from
32.4 to 25.4 wt% and that of NCG decreased from 24 to 7.8 wt% as the
reaction temperature increased from 400 to 450 ◦ C. Above 450 ◦ C, both
CB and NCG tended to increase because of secondary reactions. In the
case of simulation, the yield of WTPO decreased from 60.6 to 51.4 wt%
with increasing the reaction temperature. Conversely, the yield of NCG
increased from 5.9 to 18.9 wt%, and the CB yield slightly increased from
33.5 to 34.4 wt%. Comparing the experiment and simulated results, it
was confirmed that the product yields after 450 ◦ C shows a similar trend.
Fig. 7 shows the water content, viscosity, and HHV of WTPO as a
function of the reaction temperature. Viscosity is one of the important
parameters affecting the operating condition of injection system [62]. A
viscometer (Brookfield, Model DV2TLV) was used to measure the vis­
cosity of WTPO. With reference to other researches, the viscosity was
measured at 40 ◦ C [46]. Because the waste tire sample had a low water Fig. 9. Yield of pyrolysis products with respect to superficial gas velocity.
content, the water content of the WTPO was also less than 5 wt% at all
temperature ranges; in particular, at 500 ◦ C, the lowest water content of transfer efficiency decreased due to the strong particle ejection, and the
1.2 wt% was achieved. The viscosity of WTPO was inversely propor­ sample did not react sufficiently. Besides, a very high superficial gas
tional to the water content, and the highest viscosity was 40 cP at velocity reduced the yield of WTPO due to the incomplete condensation
500 ◦ C. The highest HHV was 44.7 MJ/kg at 500 ◦ C. WTPO has an HHV of the pyrolysis gas, which increased NCG yield in the fast pyrolysis
equivalent to that of fossil fuels such as gasoline, diesel, and heavy oil; process [65]. A similar trend was observed in previous studies [64,66,
therefore, WTPO has been confirmed to have a high potential as an 67]. The CB yield decreased from 41.3 to 28.2 wt% as the U/Ums
alternative fuel [63]. As a result of the fast pyrolysis experiment, with increased, and NCG yield increased from 12.3 to 27.1 wt%. Fig. 10
respect to the reaction temperature, the WTPO yield was the highest at shows the water content, viscosity, and HHV of WTPO with respect to
450 ◦ C, but the HHV was the highest at 500 ◦ C. Therefore, to select the the superficial gas velocity. The highest water content of the WTPO was
optimal temperature, the energy efficiency of the WTPO was analyzed, 3.7 wt% at U/Ums = 1.4, and the HHV and viscosity showed opposite
as shown in Fig. 8, and the calculation method is shown in Equation (2). trends to that of water content. The HHV was lowest at U/Ums = 1.4
Energy efficiency = (HHV × yield of WTPO) / (HHV of raw material) × 100 (43.5 MJ/kg). The viscosity reached a peak at U/Ums = 1.1 (34 cP)
before decreasing. Fig. 11 shows the energy efficiency of WTPO with
(2)
respect to the superficial gas velocity. As the U/Ums increased from 0.8
As the reaction temperature increased from 400 to 450 ◦ C, the energy to 1.1, the energy efficiency increased from 56.9% to 82.1%. Subse­
efficiency of WTPO increased, and as the reaction temperature increased quently, the energy efficiency decreased to 54.5%. Therefore, the con­
further to 550 ◦ C, the energy efficiency decreased. The highest energy dition of U/Ums = 1.1, which is the jet-in spouted bed regime, is the most
efficiency was 82.2 wt% at 450 ◦ C. The maximum HHV and minimum optimal superficial gas velocity.
moisture content were obtained at a reaction temperature of 500 ◦ C, but
the highest energy efficiency was obtained at 450 ◦ C; therefore, the
3.4. Characteristics of WTPO with respect to feeding rate
optimal temperature was selected as 450 ◦ C.
Figs. 12–14 show the characteristics of fast pyrolysis depending on
3.3. Characteristics of WTPO with respect to superficial gas velocity
the feeding rate (0.5–1.5 kg/h) at the optimal reaction temperature and
superficial gas velocity of 450 ◦ C and U/Ums = 1.1. When the feeding
The vapor residence time is a major factor that affects the yield of fast
rate was increased from 0.5 to 1 kg/h, the yield of WTPO increased from
pyrolysis products. Fast pyrolysis maximizes the recovery rate of py­
37.5 to 66.9 wt%. When the feeding rate was increased further to 1.5 kg/
rolysis oil with a short vapor residence time of less than 2 s. Vapor
residence time can be controlled by varying the amount of supplied
fluidizing gas [61]. To improve the efficiency of the CSBR, it is important
to conduct the process in the optimal velocity regime. The characteris­
tics of the WTPO were investigated by changing the superficial gas ve­
locity to 0.8, 1.1, and 1.4, based on the Ums derived from the pressure
drop experiment. The reaction temperature was 450 ◦ C, which was
derived as the optimal temperature in the previous experiment. Fig. 9
shows the yields of the fast pyrolysis products with respect to the su­
perficial gas velocity of nitrogen, which was the fluidizing gas. As the
U/Ums of nitrogen in the reactor increased from 0.8 to 1.1, the yield of
WTPO increased from 46.3 to 67.0 wt%. Subsequently, when the U/Ums
was further increased to 1.4, the yield of WTPO decreased to 44.7 wt%.
According to Park et al. [64], it is classified as a jet-in spouted bed
regime when U/Ums = 1.1 and a spouting regime when U/Ums = 1.4. In
jet-in spouted bed regime, as the superficial gas velocity increased,
material mixing in the reactor became vigorous and the vapor residence
time decreased, thereby suppressing secondary reactions. However, Fig. 10. Water content, viscosity, and HHV of WTPO with respect to superficial
when the flow regime was a spouting regime, the solid mixing and heat gas velocity.

6
J.G. Hwang et al.
Fig. 11. Energy efficiency of WTPO with respect to superficial gas velocity.
Fig. 12. Yield of pyrolysis products with respect to feeding rate.
Fig. 13. Water content, viscosity, and HHV of WTPO with respect to
feeding rate.
h, the yield decreased to 47.2 wt%. The CB yield increased from 26.3 to
46.4 wt% when the feeding rate was increased, and the yield of NCG
decreased from 36.2 to 6.4 wt%. As the feeding rate of the sample
7
Energy 262 (2023) 125519
Fig. 14. Energy efficiency of WTPO with respect to feeding rate.
increased, the amount of generated pyrolysis vapor increased, and the
vapor residence time is shortened, thereby increasing the yield of WTPO.
However, at a very high feeding rate, the yield of WTPO decreased and
the yield of CB increased because of the lack of sufficient heat for the
thermal decomposition of the sample [68,69]. As shown in Fig. 13, the
feeding rate did not significantly affect the HHV of the WTPO. The water
content tended to decrease and then increase as the feeding rate
increased, and the HHV and viscosity tended to increase and then
decrease as the feeding rate increased. According to Uzun’s study [70], a
low heating rate promotes secondary dehydration and increases the
water content in WTPO. As a result, it was confirmed that a high heating
rate was necessary to decompose a large sample. The highest energy
efficiency of the WTPO was 82.1% at 1 kg/h.
In the fast pyrolysis experiment, the conditions with the highest
energy efficiency of WTPO were chosen as the optimal condition, which
comprised a reaction temperature of 450 ◦ C, U/Ums = 1.1, and feeding
rate = 1 kg/h. Table 4 lists the properties of the WTPO produced under
optimal conditions and other pyrolysis oils. The WTPO mainly
comprised carbon (85.44 wt%), with 10.31 wt% hydrogen, 2.67 wt%
oxygen, 1.05 wt% sulfur, and 0.54 wt% nitrogen. Additionally, the
water content was 2.5 wt% and the HHV was 43.8 MJ/kg. WTPO has a
higher fuel quality than lignocellulosic pyrolysis oil because it contains
1.5 times more carbon and hydrogen than lignocellulosic pyrolysis oil,
and has lower oxygen content. It has similar characteristics to heavy fuel
oil and has higher HHV than that of waste plastic pyrolysis oil. Hence,
WTPO is most suitable for an alternative fuel among them. However,
research on reducing the sulfur and water contents is necessary for
practical applications.
3.5. D-limonene recovery from the WTPO
Before the distillation experiment, D-limonene yield was calculated
based on 1000 g of raw waste tires. Table 5 shows the yield of D-limo­
nene in WTPO considering the yield of WTPO by experimental condi­
tions. The D-limonene concentration of WTPO produced under the
optimal conditions (case 2) of the fast pyrolysis experiment was 1.2349
wt%. There were conditions with a higher D-limonene concentration
than this value, but the WTPO yield was low, so the D-limonene yield
was the highest in case 2 in the end. Fig. 15 shows the D-limonene yield
in WTPO with respect to fast pyrolysis conditions. All of the D-limonene
yields were normalized on the basis of optimal conditions (450 ◦ C, U/
Umf = 1.1, 1 kg/h). As a result of fast pyrolysis experiment and D-
limonene yield analysis, it was confirmed that case 2 was the optimal
condition. WTPO produced in case 2 was distilled to obtain high-purity
J.G. Hwang et al. Energy 262 (2023) 125519

Table 4
Comparison of WTPO and other pyrolysis oils.
Properties WTPO Heavy fuel oil Waste plastic pyrolysis oil [71] Larch pyrolysis oil [47] M. sacchariflorus [72]

Elemental analysis (wt.%) C 85.44 81.95 87.9 42.65 49.1

H 10.31 10.43 8.5 5.46 7.2
O 2.67 7.21 3.3 51.64 43.0
N 0.54 0.21 0.14 0.25 0.7
S 1.05 0.2 0.16 – –
Water content (wt.%) 2.5 0.1 0.1 25.9 17.4
HHV (MJ/kg) 43.8 44.2 38.3 16.8 19.3

Table 5
D-limonene yield with respect to fast pyrolysis conditions.
Case Reaction temperature Superficial gas velocity (U/ Feeding rate (kg/h) Waste tires (g) WTPO yield (g) D-limonene D-limonene yield (g)
(◦ C) Umf) Concentration (wt.
%)

1 400 1.1 1 1000 434.46 1.0175 4.42

2 450 1.1 1 1000 670.11 1.2349 8.28
3 500 1.1 1 1000 435.20 1.4323 6.23
4 550 1.1 1 1000 357.91 0.8858 3.17
5 450 0.8 1 1000 464.31 1.7439 8.10
6 450 1.4 1 1000 447.25 0.9474 4.24
7 450 1.1 0.5 1000 375.04 0.4342 1.63
8 450 1.1 1.5 1000 471.77 1.5083 7.12

(Based on 1000 g of waste tires).

Fig. 15. D-limonene yield in WTPO with respect to fast pyrolysis conditions.
Fig. 16. Recovery efficiency with respect to distillation time.

D-limonene.
and other compounds, but distilled oil mainly consists of D-limonene.
To recover high value-added D-limonene from WTPO, optimal
Through distillation of WTPO, high-purity D-limonene could be ob­
distillation conditions were determined by changing the distillation time
tained. Table 6 shows the GC-MS results of WTPO and distilled oil.
in a vacuum distillation recovery apparatus. The recovery efficiency was
D-limonene concentration of WTPO produced by optimal fast pyrolysis
calculated using equation (3):
conditions was 1.23 wt%. As the distillation time increased from 1 to 4 h,
Recovery efficiency = (mass of distilled oil) / (mass of vapor gas) × 100 the D-limonene content of the distillation oil increased from 2.99 wt% to
(3) a maximum of 8.01 wt%, but D-limonene was not detected after 4 h. As
described above, because D-limonene is highly volatile, when distilling
The mass of vapor gas was calculated as the weight difference of
for more than 4 h, all D-limonene in the distillation oil evaporated, and it
WTPO before and after distillation. As shown in Fig. 16, when the
was determined that only low-volatile hydrocarbon substances
distillation time was increased from 1 to 4 h, the recovery efficiency
remained in the distillation oil. Based on the distillation results, it was
increased from 36.5% to 70.5%. After 8 h, the recovery efficiency
confirmed that distillation for 4 h was optimal for recovering distillation
decreased to 31.0%. For D-limonene, which has strong volatility, when
oil containing high-purity D-limonene from WTPO. Under optimal
the distillation time is more than 4 h, the evaporation amount increases
conditions, the distilled oil, which contained up to 6.5 times D-limonene
more than the extraction amount; therefore, the recovery efficiency
compared to WTPO was recovered. Additionally, distillation for >4 h
decreased after 4 h [73]. To analyze the D-limonene content of WTPO
reduced the D-limonene yield. After production and distillation under
and distilled oil, GC-MS analysis was performed as shown in Fig. 17. A
optimal conditions (450 ◦ C, U/Umf = 1.1, 1 kg/h, 4 h distillation), the
calibration curve was first derived using (+)-limonene as an external
yield of D-limonene is 5.65 g, which is 0.56 wt% based on 1000 g of raw
standard material. As shown in Fig. 17, WTPO consists of D-limonene

8
J.G. Hwang et al.
Fig. 17. GC/MS diagram of WTPO (a) and distilled oil (b).
Table 6
GC-MS results of WTPO and distilled oil (450 ◦ C, U/Umf = 1.1, 1 kg/h).
WTPO Distilled oil
D-limonene Distillation Time (h) D-limonene
Concentration (wt.%) Concentration (wt.%)
1.2349 1 2.9907
2 3.5001
4 8.0096
8 N/D
waste tires. Li et al. [42] pyrolyzed scrap tires in a rotary kiln, and the
maximum limonene yield in WTPO was about 2.7 wt%, which was
higher than the results of this study. However, since this is a result
including both D-limonene and L-limonene, the actual difference is not
considered to be significant. However, additional research is needed to
improve the yield of D-limonene in order to improve the economic
competitiveness of the waste tire pyrolysis process.
3.6. Energy efficiency improvement by fast pyrolysis of waste tires
Fig. 18 shows the comparison of waste tire energy recovery methods.
The direct energy recovered from fast pyrolysis, an endothermic process,
is lower than energy from direct combustion [46]. But, it is difficult to
directly compare the incineration and fast pyrolysis processes. In terms
of energy, the fast pyrolysis products such as WTPO, CB, and high
value-added substances have great potential for renewable energy as
well as renewable materials. Bi, Rongshan, et al. [74] conducted
techno-economic analysis on the pyrolysis process of waste tire. A
simulation model was established for the entire process of fast pyrolysis,
including pretreatment and pyrolysis of waste tires, processing of
WTPO, and activation of CB, etc. From the results, when the capacity of
9
Energy 262 (2023) 125519
Fig. 18. Comparison of waste tire energy recovery methods.
the plant for waste tires reaches 50,000 ton/year, investment payback
period is 3.6 years. In general, considering that the investment payback
period of incineration is more than 10 years, the economic feasibility of
fast pyrolysis of waste tires is high. That means the energy effect of the
fast pyrolysis method is very high. Furthermore, for high value-added
substance, the price of WTPO is about 400 $/ton, but the price of
D-limonene is more than 10,000 $/ton, which is 25 times higher than
WTPO [35]. Therefore, fast pyrolysis process could be considered first in
energy production from waste tire.
4. Conclusions
In this study, D-limonene was recovered by applying eco-friendly fast
pyrolysis to waste tires and distilling the produced WTPO. The reaction
temperature, superficial gas velocity, and feeding rate were explored as
experimental variables. The reaction temperature has the greatest in­
fluence on the yield of the products. The highest yield of WTPO was
67.0 wt% at 450 ◦ C. The quality of WTPO was the best with an HHV of
44.7 MJ/kg and a water content of 1.2 wt% at 500 ◦ C. However, 450 ◦ C
was set as the optimal condition based on energy efficiency. In the case
of highly volatile D-limonene, 4 h was the optimal duration because the
amount of evaporation is greater than the amount of extraction when the
distillation time is greater than 4 h. Considering even the WTPO yield,
the optimal conditions for producing D-limonene are 450 ◦ C, U/Umf =
1.1, 1 kg/h, 4 h distillation. Under these conditions, the yield of D-
limonene is 5.65 g, which is 0.56 wt% based on 1000 g of raw waste
tires. In summary, the fast pyrolysis process developed in this study can
treat waste tires in an eco-friendly manner and produce CB and WTPO
comparable to heavy fuel oil. In addition, high economic efficiency can
be achieved through the recovery of D-limonene by using fractional
distillation technology. Since the technology to recover high value-
added materials from WTPO is in the early stage, this study can pro­
vide guidelines for future scale-up research.
Credit author statement
Jae Gyu Hwang: Methodology, Investigation, Validation, Writing.
Byeong Kyu Lee: Methodology, Investigation, Data analysis. Myung
Kyu Choi: Investigation, Data curation. Hoon Chae Park: Validation,
Data curation. Hang Seok Choi: Conceptualization, Resources, Writing-
Review & Editing, Supervision, Project administration, Funding
acquisition.
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.
J.G. Hwang et al. Energy 262 (2023) 125519

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