catalysts

Article
Conditions Optimization and Physiochemical Analysis of Oil
Obtained by Catalytic Pyrolysis of Scrap Tube Rubber Using
MgO as Catalyst
Riaz Muhammad 1,2, * , Yousaf Ali 1 , Younes Messaddeq 3 , Haroon ur Rashid 4 ,
Marco Antonio Utrera Martines 4 , Muhammad Naveed Umar 5 , Sher Wali Khan 6 and Ali Riaz 1,3

1 Sarhad University of Science & Information Technology, Peshawar 25000, Pakistan;

[email protected] (Y.A.); [email protected] (A.R.)
2 Leibniz-Institute for Catalysis, University of Rostock, D-18059 Rostock, Germany
3 Centre for Optics, Photonics and Laser, University of Laval, 2375 rue de la Terrasse,
Quebec, QC G1V 0A6, Canada; [email protected]
4 Institute of Chemistry, Federal University of Mato Grosso do Sul, Cidade Universitaria, Campo Grande
79074-460, MS, Brazil; [email protected] (H.u.R.); [email protected] (M.A.U.M.)
5 Department of Chemistry, University of Malakand, Chakdara 18800, Pakistan; [email protected]
6 Department of Chemistry, Shaheed BB University Sheringal, Sheringal 18050, Pakistan;
[email protected]
* Correspondence: [email protected]; Tel.: +92-311-9830166

Abstract: Motor vehicles scrap tires and tube rubbers generate a large amount of waste with different



characteristics and compositions, contaminating the environment when not properly disposed. Waste


inner tube rubber (isobutylene isoprene) representing a threat to the environment can be used as
Citation: Muhammad, R.; Ali, Y.; valuable source of energy. Waste inner tube rubber was pyrolyzed thermally under atmospheric
Messaddeq, Y.; ur Rashid, H.;
pressure both with and without catalyst. Parameters of temperature, time, and catalyst weight
Antonio Utrera Martines, M.; Naveed
were optimized for catalytic and thermal pyrolysis of isobutylene-isoprene rubber into liquid fuel,
Umar, M.; Khan, S.W.; Riaz, A.
using MgO as catalyst. It was found that one-hour heating time at 350 ◦ C using 2 g catalyst (MgO)
Conditions Optimization and
constitutes a suitable parameter for the maximum conversion of scrap inner tube rubber into oil.
Physiochemical Analysis of Oil
Obtained by Catalytic Pyrolysis of
The oil obtained was characterized by physical and chemical tests. Among the physical tests,
Scrap Tube Rubber Using MgO as Density, specific gravity, viscosity, kinematic viscosity, analine point and flash point were determined
Catalyst. Catalysts 2021, 11, 357. according to IP and ASTM standard valves. The physical tests indicate the presence of aromatic
https://doi.org/10.3390/ and olefinic hydrocarbons. Among the chemical tests, the phenol test, bromine number, bromine
catal11030357 water test, and KMnO4 tests were conducted. The chemical tests are also the support of physical tests
conducted. The physical and chemical tests indicate that the oil obtained is a mixture of kerosene,
Received: 27 January 2021 diesel, and light oil and could be used for fuel purposes.
Accepted: 5 March 2021
Published: 10 March 2021 Keywords: pyrolysis; scrap rubber; liquid fuel; magnesium oxide; catalysis

Publisher’s Note: MDPI stays neutral

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1. Introduction
iations.
Human lifestyle is improving rapidly, resulting in the increased demand for high-
end freeways and highways, consequently increasing the demand for motor vehicles
around the world. The rapid expansion of automobile business has therefore brought
up some environmental drawbacks where handlings of waste tires/tubes are one of the
Copyright: © 2021 by the authors.
fast-growing issues [1]. European Tyre & Rubber Manufacturers’ Association (ETRMA)
Licensee MDPI, Basel, Switzerland.
statistics reported that 1400 million tires are being produced, generating 17 million tons of
This article is an open access article
used tires/tube waste every year [2].
distributed under the terms and
conditions of the Creative Commons
Millions of tires/tubes are either thrown away or buried all over the world which is
Attribution (CC BY) license (https://
considered a threat to the ecosystem. As per a concise study, there would be 5000 million
creativecommons.org/licenses/by/
tires discarded annually by the year 2030 [3]. These scrap tire/tube rubber due to their
4.0/).

Catalysts 2021, 11, 357. https://doi.org/10.3390/catal11030357 https://www.mdpi.com/journal/catalysts

Catalysts 2021, 11, 357 2 of 13

non-biodegradable nature repeatedly leads to black pollution, bestowing a threat to the

environment by causing land occupation, fire risk, and many more [4].
Scraped inner tube is the type of synthetic rubber, that has the capability of retaining
air, is mostly used by the automobile and alike industry. It is a co-polymer of 97–98%
isobutylene and 2–3% isoprene prepared at low temperature (100 ◦ C) via Friedel-Craft’s
catalyst [5,6].
The combination of various factors like resistance to oxidation, ozone, bacteria and
solar radiation makes butyl rubber (BR) a good material for making tire as well as inner
tube by automobile industry. Regular butyl rubber is the most preferably used material for
inner tubes in a range of lightweight to lifestyle bicycles as well as luxury motorcycles.The
development of Butyl rubber can be traced back to the work of Gorianov and Butlerov
in early 1870s, and later Otto (1927) in an attempt to yield low molecular weight oily
polymers by isobutylene polymerization at room temperature in the presence of sulfuric
acid and BF3 .
Later on, in 1930, I.G. Farben workers succeeded in producing higher molecular
weight polymers by reacting a dilute hydrocarbon solution of isobutylene with BF3 at very
low temperatures. In a similar fashion a variety of Lewis acids can be used to initiate such
kind of polymerization [5,6].
But these carbon based rubber materials were later on became one of the main environ-
mental issues concerning their proper recycling. Gomes and his coworkers has previously
reported various toxicological constituents of rubber granules obtained from used tires [7].
Among several approaches, pyrolysis was considered a plausible approach to deal with
such materials for carbon black production as well as alternative fuel resources [8,9].
Czajczynska and co-workers [10] stated that waste tire can be recycled to a useful
fuel so as the mentioned risks to human health (many diseases) as well as to environment
(wasted tires dumps as habitats for mosquitos and rodents) can be reduced. Although, oil
obtained from the recycling of these rubbers may generally contain a variety of compounds
and cannot be used directly as fuel but can be used as an alternative to diesel [11].
In this regard several approaches were adopted by different researchers around the
globe. Lin and his coworkers [12] reported the thermo-gravimetric conversion (temperature
range of 127–677 ◦ C) of scrape Styrene-butadiene rubber (SBR) in to a useful energy source.
These results were supported by Miranda and his co-workers [13] while exploring
the effect of temperature on the mechanism of tire waste’s pyrolysis. They entrenched the
effect of temperature on pyrolysis reactions of tire wastes. In another study R. Edwin Raj
and his fellow researchers [14] used fluidized bed combustion system where they reported
that slower feed rate at 440 ◦ C may increase the residence time in reactor for maximum oil
yield. They investigated physical and chemical properties of product oil (pyrolysis as well
as distilled oil) along with the evolved gases during the process to assess the suitability of
their product as conventional fuel.
Telnov and his co-workers [15] studied the degradation of butyl rubber via electron
beam at 6–10 MeV. The degraded material was re-used to formulate the diaphragm for
fabric and roofing purpose.
M. En and his co-workers [16] reported the use of gamma irradiation for degrading
iso-butylene-isoprene rubber where the effect of dose rate on degradation was studied.
Their findings indicate that samples were better degraded at lower dose rate and under
oxidizing atmosphere compared to the degradation at higher dose rate and under ni-
trogen atmosphere. Perera and fellows [17] investigated the gamma radiation effect on
polypropylene blends with sTyrene-butadiene-sTyrene co-polymers where they studied the
generation and decay of free radicals using electron spin resonance for the establishment
of kinetics involved in the process.
M. Hassan and his fellows [18] described the devulcanization of passenger car tire’s
rubber thru mechanical-chemical process where they measured the sol content as well as
get content of the devulcanized products. J. Shah and co-worker [19] studied the effect
of Calcium carbide catalyst on distribution of pyrolysis product of rubber where they
Catalysts 2021, 11, 357 3 of 13

described that temperature increase in the presence of Calcium carbide catalyst increases
liquid fraction as well as total evolved gases while decreasing char yield. They reported
that their product liquid had high calorific value; GCV (42.8 MJ kg−1 ) with boiling point
of 320 ◦ C. Their results indicated that viscosity, freezing point, specific gravity and diesel
index of the liquid product were comparable to diesel fuel.
A review presented by A. Quek and his co-workers reveals [20] that pyrolytic oil
products obtained from various types of waste tires as well as their pyrolysis operating
conditions may yield useful chemicals such as limonene, aromatic benzene and alike
compounds. Similar findings were reported by G. Choi and co-workers [21] who used a
fixed bed reactor to pyrolyze waste tire rubber at temperature ranging for 500–800 ◦ C. They
reported the presence of aromatic hydrocarbons, limonene along with some heteroatom-
containing compounds like 2,4-dimethylquinoline and benzothiazole in their pyrolyzed
oil products. G. I. Danmaliki and T. A. Saleh [22] investigated conversion of scrap tires
into activated carbon where nitric acid was used to oxidize the functional groups on the
surface of the product. The carbonization was optimized at 500 ◦ C along with activation
temperature at 900 ◦ C yielding sorbent with a surface area of 473 m2 /g.
B.C. Yu and fellows [23] reported a low cost electrochemical means of recycling
waste rubber.
R. Vihar and his fellows [24] investigated the use of pyrolysis oil produced from waste
tires in a turbocharged heavy-duty engine, where they reported that their product oil can
resourcefully be used as a fuel in a turbocharged non-intercooled engine. Their findings
suggest the use of pyrolyzed oil for power generation.
S. Luo and Y. Feng [25] utilized the heat of blast-furnace slag as waste energy recycling
for production of oil and gas form waste tire pyrolysis where they reported the upgradation
of oil quality by increased construction of derived oil and gases such as H2 as well as CO
during pyrolysis.
A. H. Ahoor and N. Z. Atashbar [26] used MgCl2 catalyst in a batch reactor for
pyrolysis of waste tire under inert atmosphere, where they optimized conditions to 407.3 ◦ C
pyrolysis temperature, 12.5 mm particle size, 133.7 mL min−1 flow rate for 1800 s pyrolysis
time using 11.5 wt% of catalyst. They reported that the product oil with physical properties
such as cetane number, viscosity, and density comparable to the commercial diesel fuel can
be used as alternative fuel. Their results indicate that MgCl2 was helpful in reduction of
the sulfur content of the final product.
H. Aydin and co-workers [27] reported the use of Ca(OH)2 as catalyst for pyrolysis of
waste tire rubber under nitrogen atmosphere, where they described the decrease in sulfur
content of the product oil.
E. Yazdani et al. [28] converted waste tire into a distillate mixture of light naphtha
(14%), heavy naphtha (4%) and middle distillate (36%) in a rotating kiln reactor at tempera-
ture ranging from 400 ◦ C to 1050 ◦ C under inert atmosphere.
Literature reveals that scrap tire rubber is pyrolyzed using a variety of catalysts
including silica-alumina, mesoporous materials (MCM-type), clays (ZSM-5), zeolites and
alike materials. Some synthetic zeolites were also used by different researchers but they
are somehow expensive that affect the final cost for industry [29,30]. Shah and co-workers
reported the use of MgO catalyst for tire rubber conversion into useful hydrocarbons
optimizing temperature and reaction time where they have reported 34% total liquid at
350 ◦ C [31].
In the present study, the use of economic and easily available MgO catalyst for the
conversion of waste tube rubber with well optimized conditions of temperature, time, and
mass of catalyst is being reported where its influence on the composition and improved
yield of derived oil is investigated. The obtained product oils were investigated via various
physical and chemical tests in order to ensure its potential use as fuel.
Catalysts 2021, 11, x FOR PEER REVIEW 4 of 14

Catalysts 2021, 11, 357

proved yield of derived oil is investigated. The obtained product oils were investigated4 of 13
via various physical and chemical tests in order to ensure its potential use as fuel.

2. Results and Discussion

2. Results optimizations
Condition and Discussionfor the yield of catalytic cracking of tube rubber were per-
formed in Condition
a systematic optimizations for the yield
way, where physical of catalytic
and chemical testscracking
of the oilofproducts
tube rubber
were were
done.performed in a systematic way, where physical and chemical tests of the oil products
were done.
2.1. Temperature Optimization for Catalytic Cracking of Tube Rubber
2.1. Temperature Optimization for Catalytic Cracking of Tube Rubber
Temperature optimization results of tube rubber are shown in Table 1 and in Figure
1. It can beTemperature optimization
seen that an increase results of tube
in temperature fromrubber
250 toare
350shown in Table 1 and
°C subsequently in Figure 1.
increases
It can be seen that an increase in temperature from 250 to 350 ◦ C subsequently increases the
the amount of liquid while decreases char (solid). The total conversion of tube rubber is
99.6%amount of liquid
at 350◦ °C. while decreases
This indicates char (solid).
the completion The totalatconversion
of reaction 350 °C. Theofmaximum
tube rubber is 99.6%
con-
◦ C. The maximum conversion of
at 350 C. This indicates the completion of reaction at 350
version of oil took place at◦ 350 °C and was selected as the optimum temperature for fur-
oil took place at 350 C and was selected as the optimum temperature for further work.
ther work.

Table 1. Temperature
Table 1. Temperature Optimization
Optimization for Cracking
for Catalytic Catalytic of
Cracking of Tube Rubber.
Tube Rubber.
S.No Temp ◦ C) % (L) ± S.D % (G) ± S.D % (G)T.±Con T. Con ± S.D
S.No Temp (°C) % (L) ± S.D %( (S) ±S.D % (S)
±S.D S.D ±S.D
1 250 23.84 ± 1.38
1 23.84 ± 1.38 17.30
58.73 ± 1.60
250 ± 1.60
± 1.34
58.73 ± 1.34± 0.21
17.30 99.88 99.88 ± 0.21
2 300 30.26 ± 0.14
2 42.10 ± 0.10
300 30.26 ± 0.14 27.64 ± 0.04
42.10 ± 0.10 27.64 100.0
± 0.04± 0.00
100.0 ± 0.00
3 350 51.66 ± 0.56
3 30.66 ± 0.76
350 51.66 ± 0.56 17.67 ± 0.50
30.66 ± 0.76 17.67 99.60
± 0.50± 0.41 99.60 ± 0.41
“Temp” stands for temperature, “L” “Temp”
for liquid “S”forfor
stands solid, “G”
temperature, for
“L” forgas, “T.
liquid “S”Con” for “G”
for solid, totalforconversion
gas, “T. Con”and “S.D”
for total stands for
conversion and “S.D”
standard deviation. stands for standard deviation.

Char
Liquid
60 Gas
55

50

45
Conversion (%)

40

35

30

25

20

15
260 280 300 320 340 360 380 400
o
Temperature ( C)

Figure 1. Temperature Optimization for Catalytic Cracking of Tube Rubber.

Figure 1. Temperature Optimization for Catalytic Cracking of Tube Rubber.
Other authors also obtained results in the similar range but using high temperature of
Other authors
pyrolysis. Theyalso obtained
obtained results inliquid
maximum the similar
yield range
(55 wt%)but at
using high temperature
a pyrolysis temperature of
◦
of pyrolysis. They the
550 C while obtained maximum
char yield was as liquid
low asyield
33 wt%(55and
wt%) theatgas
a pyrolysis
yield wastemperature
around 11 wt% of [32].
550 °C while the char
Cunliffe andyield was [33]
Williams as low as 33 wt%
reported and the
58.2 wt% gas◦ C
at 475 yield
which waswas
around 11 wt%
adversely affected
[32]. by the increase in temperature to 53.1 wt% at 600 ◦ C. Murillo and his fellows [34] reported
Cunliffe and Williams
an increased yield from[33] reported
42.24 wt% to58.2
60.02% 475◦°C
wt%atat425 which
C but was adversely
a decrease at 500 ◦ C.
affected
to 54.1 wt%
by theInterestingly,
increase in they
temperature to 53.1 wt% at 600 °C. Murillo and his fellows
reported a decrease in char from 50.67 to 26.41 wt% at 450 C and ◦
[34] re- then
ported an increased
remain constant.yield
Quefrom 42.24
and his wt% to 60.02%
co-workers at 425 °C
[35] reported but oil,
17.7% a decrease
49.0% gasto and
54.133.3%
wt% char
at 500from
°C. Interestingly, they reported
catalytic conversion waste tires at 430 ◦in
a decrease char from
C using ZSM-5 50.67 to 26.41
zeolite underwt% at 450
inert °C
atmosphere.
Murugan et al. [36] performed pyrolysis of waste tires from 450 to 650 ◦ C with heating rate
of 5 ◦ C min−1 for 2 h and 30 min. They reported 55% liquid fraction and 10% of gas as
their products. Kar [37] investigated pyrolysis of used tires reporting 60.0 wt% maximum
oil yields at 425 ◦ C, where it decreased to 54.12 wt% at 500 ◦ C with a decrease in char
 10% of gas as their products. Kar [37] investigated pyrolysis of used tires reporting 60.0
wt% maximum oil yields at 425 °C, where it decreased to 54.12 wt% at 500 °C with a de-
crease in char from 50.67 to 26.41 wt% and increase of gas from 2.99 to 20.22 wt%. Liter-
ature reveals that increase in temperature consequently decreased the TPO yield, how-
Catalysts 2021, 11, 357
ever 400–450 °C in the optimum temperature range for increased tire pyrolysis oil yield 5 of 13
[38].
The results confirm that with variations in temperature, changes not only occur in
the percent conversion but also in the nature of the products. It was expected that there
wouldfrom 50.67
be an to 26.41
increase inwt% and increase of
the temperature gas from
polarity 2.99catalyst
of the to 20.22 due
wt%.toLiterature reveals
the increase in that
increase
vibrational in temperature
energies consequently
of the catalyst. Thus, decreased the TPO also
charge induction yield,increases, 400–450 ◦ C
however resulting inin the
fasteroptimum
reaction. temperature range for increased tire pyrolysis oil yield [38].
The results confirm that with variations in temperature, changes not only occur in the
2.2. Weight of conversion
percent but also infor
Catalyst Optimization theCatalytic
nature of the products.
Cracking of TubeItRubber
was expected that there would
be an 2increase
Table in the2temperature
and Figure shows that polarity
amount ofof the catalyst
liquid due toand
increases the that
increase in vibrational
of solid de-
energies of the catalyst. Thus, charge
creases with increase of weight of catalyst. induction also increases, resulting in faster reaction.

2.2. Weight of Catalyst Optimization for Catalytic Cracking of Tube Rubber

Table 2. Weight of Catalyst Optimization for Catalytic Cracking of Tube Rubber.
Table 2 and Figure 2 shows that amount of liquid increases and that of solid decreases
S.No W(g) % (L) with
±S.Dincrease of weight
% (S) ±
ofS.D
catalyst. % (G) ±S.D T.Con ±S.D
1 0 8.46 ± 0.18 79.46 ± 0.42 12.06 ± 0.589 100 ± 0.00
2 0.5 6.37 2. Weight of Catalyst
45.89 ±Table 37.48 ± Optimization
3.07 for Catalytic
16.64 ± Cracking
3.32 of Tube Rubber.
100 ± 0.00
3 1 51.66 ± 0.56 30.6 ± 0.76 17.67 ± 0.50 99.66 ± 0.41
S.No W(g) % (L) ± S.D % (S) ± S.D % (G) ± S.D T.Con ± S.D
4 1.5 58.82 ± 2.71 24.8 ± 1.29 16.31 ± 2.04 100 ± 0.000
1 0 8.46 ± 0.18 79.46 ± 0.42 12.06 ± 0.589 100 ± 0.00
5 2 62.77 ± 1.76 20.26 ± 0.64 16.96 ± 1.13 100 ± 0.000
2 0.5 45.89 ± 6.37 37.48 ± 3.07 16.64 ± 3.32 100 ± 0.00
“W” stands for weight of catalyst, “L” for liquid “S” for solid, “G” for gas, “T.Con” for total conversion and “S.D” stands for
standard deviation 3 1 51.66 ± 0.56 30.6 ± 0.76 17.67 ± 0.50 99.66 ± 0.41
The release4 of gases is1.5almost constant
58.82 ± with
2.71 0.5–2.0
24.8 ±g 1.29
of catalyst.
16.312 ±g of
2.04catalyst
100 was
± 0.000
selected as optimum
5 weight 2 for cracking of butyl
62.77 ± 1.76 rubber because
20.26 ± 0.64 it produces
16.96 ± 1.13 approxi-
100 ± 0.000
mately“W”the same
stands amount
for weight of char
of catalyst, “L”(carbon
for liquidblack) as present
“S” for solid, in the
“G” for gas, formulation
“T.Con” of butyl
for total conversion and “S.D”
inner stands
tube [5,6].
for standard deviation

Liquid
Char
80 Gas

70

60
Conversion (%)

50

40

30

20

10

0.0 0.5 1.0 1.5 2.0

Weight of Mg (g)

Figure 2. Weight of Catalyst Optimization for Catalytic Cracking of Tube Rubber.

The release of gases is almost constant with 0.5–2.0 g of catalyst. 2 g of catalyst was
selected as optimum weight for cracking of butyl rubber because it produces approximately
the same amount of char (carbon black) as present in the formulation of butyl inner
tube [5,6].

2.3. Heating Time and Rate Optimization for Catalytic Cracking of Tube Rubber
It can be seen from the Table 3 and Figure 3 that the rate of reaction increases with
heating time.
 Figure 2. Weight of Catalyst Optimization for Catalytic Cracking of Tube Rubber.

2.3. Heating Time and Rate Optimization for Catalytic Cracking of Tube Rubber
Catalysts 2021, 11, 357 6 of 13
It can be seen from the Table 3 and Figure 3 that the rate of reaction increases with
heating time.

Table
Table 3. Heating Heating
Time3.and Rate Time and Ratefor
Optimization Optimization for Catalytic
Catalytic Cracking Cracking
of Tube of Tube Rubber.
Rubber.

S.No Time (min) %(L) ±S.D

S.No Time (min) %(S) %(L)±± S.D
S.D %(S) ± %(G)
S.D ±S.D %(G) ± S.D %T.Con ±S.D± S.D
%T.Con
1 30 29.53
1 ± 0.44 30 40.66 ± 0.31
29.53 ± 0.44 29.80
40.66 ± 0.31 ± 0.14
29.80 ± 0.14 100.0 ± 0.00± 0.00
100.0
2 60 62.76
2 ± 1.75 60 20.26
62.76± ±0.64
1.75 20.26 ±16.96
0.64 ± 1.13
16.96 ± 1.1399.99 99.99
± 0.01± 0.01
3 90 58.46 ± 1.58 21.20 ± 0.53 20.30 ± 2.09 99.99 ± 0.01
3 90 58.46 ± 1.58 21.20 ± 0.53 20.30 ± 2.09 99.99 ± 0.01
4 120 55.13 ± 0.69 21.06 ± 0.50 23.80 ± 1.17 100.0 ± 0.00
4 120 55.13 ± 0.69 21.06 ± 0.50 23.80 ± 1.17 100.0 ± 0.00
“min” stands for heating time, “L” for liquid “S” for solid, “G” for gas, “T.Con” for total conversion and “S.D” stands
“min” stands for heating time, “L” for liquid “S” for solid, “G” for gas, “T.Con” for total conversion and “S.D”
for standard deviation stands for standard deviation

Liquid
Char
65
Gas
60

55

50
Conversion (%)

45

40

35

30

25

20

30 40 50 60 70 80 90 100 110 120

Time (Minutes)

Figure 3. Heating Time and Rate Optimization for Catalytic Cracking of Tube Rubber.
Figure 3. Heating Time and Rate Optimization for Catalytic Cracking of Tube Rubber.
Maximum formation of oil (liquid) took place at 60 min heating time. The amount of
Maximum60
char after min heating
formation remains
of oil constant
(liquid) but at
took place the60amount of gases
min heating increases
time. due to of
The amount further
cracking of oil at longer time of cracking. Therefore, 60 min was
char after 60 min heating remains constant but the amount of gases increases due toselected as optimum
heating
further timeoffor
cracking oilfurther investigations.
at longer time of cracking. Therefore, 60 min was selected as op-
By using MgO as catalyst, two types of fractions, i.e., light oil and heavy oil, were
timum heating time for further investigations.
obtained and both were physically
By using MgO as catalyst, two types analyzed (Tablei.e.,
of fractions, 4). light oil and heavy oil, were
obtained and both were physically analyzed (Table 4).
Table 4. Physical properties of Liquid oil after Cracking of Tube Rubber.
Table 4. PhysicalParameters
properties of Liquid oil after Light
Cracking
Oil of Tube Rubber.
Values Heavy Oil Values
Parameters
Density (g/mL) Light Oil0.8432
Values Heavy Oil 0.9992
Values
Density (g/mL)
Specific Gravity 0.8432
0.8432 0.9992
0.9992
Specific Gravity
Viscosity (centipoises) 0.84321.63 0.99921.046
Viscosity (centipoises) 1.63 1.046
API Gravity 36.31 10.11
API Gravity 2 36.31 10.11
Kinematic (mm /sec) 1.933 1.0468
Kinematic (mm2/sec) 1.933 1.0468
Aniline Point (◦ C)
Aniline Point (°C) 69 69 52 52
◦
FlashFlash
PointPoint
(°C)( C) 39 39 45 45
Diesel
Diesel Index Index 56.71
56.71 12.6912.69
Kw Valve 9.255 6.695

The density of the light oil fraction as well as its distillation data (in the range of
180–340 ◦ C) is similar to the density of diesel fuel.
Distillation test at atmospheric pressure was carried out, for the liquids obtained in
catalytic pyrolysis at optimum conditions. The results are presented in Figures 4 and 5. It
 The density of the light oil fraction as well as its distillation data (in the range of 180–
340 °C) is similar to the density of diesel fuel.
Distillation test at atmospheric pressure9.255
Kw Valve was carried out, for the liquids 6.695obtained in
catalytic pyrolysis at optimum conditions. The results are presented in Figures 4 and 5. It
was observed thatof50%
The density volume
the light of such liquid
oil fraction as wellwas
as itseasily distillable
distillation datafraction with boiling
(in the range of 180–
Catalysts 2021, 11, 357 7 of 13
range between 80 and 200 °C which is
340 °C) is similar to the density of diesel fuel.the boiling point range specified for commercial
petrol. Laresgoititest
Distillation et al.
at[39] and Rodriguez
atmospheric et al.
pressure was [40] obtained
carried out, about
for the13% of such
liquids liquids
obtained in
from tire pyrolysis at 500 °C.
catalytic pyrolysis at optimum conditions. The results are presented in Figures 4 and 5. It
was
wasobserved
observedthatthat50%
50%volume
volumeofofsuch suchliquid
liquidwas
waseasily
easilydistillable
distillablefraction
fractionwithwithboiling
boiling
range between 80 and 200 ◦ C which is the boiling point range specified for commercial
range between 80 and 200 °C which is the boiling point range specified for commercial
petrol.
petrol.Laresgoiti
Laresgoitietetal.
al.[39]
[39]andandRodriguez
Rodriguezetetal.al.[40]
[40]obtained
obtainedabout
about13%13%ofofsuch
suchliquids
liquids
from tire pyrolysis at 500 ◦ C.
from tire pyrolysis at 500 °C.

Figure 4. Distillation of Light Oil Fraction.

Furthermore, the distillation data for light oil fraction in range of 165–230 °C bear a
resemblance to kerosene distillate while distillate in the range of 200–265 °C resembles
aromatic kerosene. The
Figure 4.Distillation
viscosity
DistillationofofLight
LightOil
and specific gravity of the product oil are also in the
OilFraction.
Fraction.
Figure
range 4.
of aromatic kerosene that further supports the distillation products.
Furthermore, the distillation data for light oil fraction in range of 165–230 °C bear a
resemblance to kerosene distillate while distillate in the range of 200–265 °C resembles
aromatic kerosene. The viscosity and specific gravity of the product oil are also in the
range of aromatic kerosene that further supports the distillation products.

Figure 5. Distillation of Heavy Oil Fraction.

Furthermore, the distillation data for light oil fraction in range of 165–230 ◦ C bear a
resemblance to kerosene distillate while distillate in the range of 200–265 ◦ C resembles
aromatic kerosene. The viscosity and specific gravity of the product oil are also in the range
of aromatic kerosene that further supports the distillation products.
Density of heavy oil fraction is near to density of heavy fuel (0.955 g/mL) oil while its
flash point is near to kerosene oil (37–65 ◦ C). The distillation data shows the presence of
light oil (80%), light naphtha (10%) and naphthalene oil (10%). 30% of heavy oil fraction
 Figure 5. Distillation of Heavy Oil Fraction.

Catalysts 2021, 11, 357 8 of 13

Density of heavy oil fraction is near to density of heavy fuel (0.955 g/mL) oil while its
flash point is near to kerosene oil (37–65 °C). The distillation data shows the presence of
light oil (80%), light naphtha (10%) and naphthalene oil (10%). 30% of heavy oil fraction
(inthe
(in therange
rangeof 158–200◦°C)
of158–200 alsoillustrates
C) also illustratesthethepresence
presenceof ofphenol
phenoloil, oil,which
whichwas wasfurther
further
confirmedby
confirmed byphenol
phenoldetermination.
determination.
Fueltests
Fuel testsshows
showsthat
thatboth
bothlight
lightandand heavy
heavy oiloil fractions
fractions are
are complex
complex mixtures
mixtures of
of hy-
hy-
drocarbons.
drocarbons.
Oil obtained
Oil obtained (mixture
(mixture of ofboth
bothlight
lightand
andheavy
heavyoil) oil)was
wasanalyzed
analyzedchemically.
chemically.FromFrom
Bromine Water Test, the solution got faint color immediately which
Bromine Water Test, the solution got faint color immediately which indicates the presence indicates the pres-
of olefin
ence s in oil.
of olefin s inFurthermore, in theinpotassium
oil. Furthermore, permanganate
the potassium permanganate test, test,
the solution lost lost
the solution its
color immediately which again confirms the presence of olefins as
its color immediately which again confirms the presence of olefins as a major componenta major component in
oil. From the calibration plot shown in Figure 6, phenol concentration
in oil. From the calibration plot shown in Figure 6, phenol concentration in each sample in each sample was
determined.
was determined. The amount of phenols
The amount found found
of phenols in heavyin oil fraction
heavy is 90 µg/100
oil fraction is 90 µmL, which
g/100 mL,
was also confirmed by the distillation fraction (158–200 ◦ C) of heavy oil. The distillation
which was also confirmed by the distillation ◦fraction (158–200 °C) of heavy oil. The dis-
temperature range forrange
tillation temperature phenolic oil is (167–194
for phenolic C).
oil is (167–194 °C).

Figure6.6.Determination
Figure Determinationof
ofphenol
phenolusing
usingAntipyratic
Antipyraticmethod.
method.

BromineNumber
Bromine Numberdetermined
determined forfor heavy
heavy oil oil fraction
fraction (70 (70 g/100
g/100 g) indicates
g) indicates the pres-
the presence
ence
of ofconcentration
high high concentration of olefinic
of olefinic compounds.
compounds.

3.3. Material
Materialand
andMethodology
Methodology
3.1. Material Used
3.1. Material Used
Magnesium
Magnesium oxide
oxide(ACS
(ACSReagent, 97%,
Reagent, Sigma-Aldrich
97%, Merck
Sigma-Aldrich KGaA,
Merck Darstadt,
KGaA, Ger-
Darstadt,
many), waste tube rubber pieces (Local Market), bromine water solution (Sigma-Aldrich
Germany), waste tube rubber pieces (Local Market), bromine water solution (Sig-
Merck KGaA, Darstadt, Germany), carbon tetrachloride (Sigma-Aldrich Merck KGaA,
ma-Aldrich Merck KGaA, Darstadt, Germany), carbon tetrachloride (Sigma-Aldrich
Darstadt, Germany), potassium permanganate (Sigma-Aldrich Merck KGaA, Darstadt,
Merck KGaA, Darstadt, Germany), potassium permanganate (Sigma-Aldrich Merck
Germany), A. R. Grade Phenols (Sigma-Aldrich Merck KGaA, Darstadt, Germany), 4–
KGaA, Darstadt, Germany), A. R. Grade Phenols (Sigma-Aldrich Merck KGaA, Darstadt,
aminoantipyrene (Sigma-Aldrich Merck KGaA, Darstadt, Germany), Potassium ferri-
Germany), 4–aminoantipyrene (Sigma-Aldrich Merck KGaA, Darstadt, Germany), Po-
cyanide (Sigma-Aldrich Merck KGaA, Darstadt, Germany), Hydrochloric acid (37%, Sigma-
tassium ferricyanide (Sigma-Aldrich Merck KGaA, Darstadt, Germany), Hydrochloric
Aldrich Merck KGaA, Darstadt, Germany), Sodium hydroxide (Sigma-Aldrich Merck
acid (37%, Sigma-Aldrich Merck KGaA, Darstadt, Germany), Sodium hydroxide (Sig-
KGaA, Darstadt, Germany), Ammonia (Sigma-Aldrich Merck KGaA, Darstadt, Germany),
ma-Aldrich Merck KGaA, Darstadt, Germany), Ammonia (Sigma-Aldrich Merck KGaA,
Ammonium chloride (Sigma-Aldrich Merck KGaA, Darstadt, Germany), Sodium thio-
Darstadt, Germany), Ammonium chloride (Sigma-Aldrich Merck KGaA, Darstadt, Ger-
sulphate (Sigma-Aldrich Merck KGaA, Darstadt, Germany), Potassium iodide (Sigma-
many), Sodium thiosulphate (Sigma-Aldrich Merck KGaA, Darstadt, Germany), Potas-
Aldrich Merck KGaA, Darstadt, Germany), Sulphuric acid (98%, Sigma-Aldrich Merck
sium iodide (Sigma-Aldrich Merck KGaA, Darstadt, Germany), Sulphuric acid (98%,
KGaA, Darstadt, Germany), Mercuric sulphate (Sigma-Aldrich Merck KGaA, Darstadt,
Sigma-Aldrich
Germany), Merckbromate-Potassium
Potassium KGaA, Darstadt, bromide
Germany), Mercuric sulphate
(Sigma-Aldrich (Sigma-Aldrich
Merck KGaA, Darstadt,
Merck KGaA, Darstadt, Germany), Potassium bromate-Potassium bromide
Germany), Sodium chloride (Sigma-Aldrich Merck KGaA, Darstadt, Germany), Starch (Sig-
indicator (Sigma-Aldrich Merck KGaA, Darstadt, Germany).
 ma-Aldrich Merck KGaA, Darstadt, Germany), Sodium chloride (Sigma-Aldrich Merck
Catalysts 2021, 11, 357
KGaA, Darstadt, Germany), Starch indicator (Sigma-Aldrich Merck KGaA, Darstadt,
9 of 13
Germany).

3.2. Instruments Used

3.2. Instruments Used
Spectrophotometer (Spectronic–20D, by Thermo Electron Corporation, Model 333183,
Spectrophotometer
Missouri, TX, USA), pH (Spectronic–20D, by ThermoMerck
meter (Sigma-Aldrich Electron Corporation,
KGaA, Model
Darstadt, 333183,
Germany),
Missouri, TX, USA),
Thermocouple pH meter
(Omega (Sigma-Aldrich
Engineering Merck
Company, KGaA, Darstadt,
Deckenpfronn, Germany),
Germany), Thermo-
digital bal-
couple (Omega Tolledo,
ance (Mettler Engineering Company,
Gießen, Deckenpfronn,
Germany), ostwald Germany),
viscometerdigital balance (Mettler
(Sigma-Aldrich Merck
Tolledo, Gießen, Germany),
KGaA, Darstadt, Germany),ostwald viscometer
and electric (Sigma-Aldrich
furnace (Nabertherm Merck
GmbH, KGaA, Darstadt,
Lilienthal, Ger-
Germany),
many). and electric furnace (Nabertherm GmbH, Lilienthal, Germany).

3.3.
3.3.Pyrolysis
PyrolysisBatch
BatchReactor
Reactor
AA Pyrex
Pyrex glass tube
glass tube of
of18
18cm
cmlength
lengthand
and3.3
3.3cm
cmwidth
widthimmersed
immersedininananautomatic
automatic
programmed
programmed electric furnace controlled via a thermocouple was used as batchreactor
electric furnace controlled via a thermocouple was used as batch reactor
Batch
Batchreactor
reactordeveloped
developedininRostock
RostockUniversity
UniversityofofGermany.
Germany.(Figure
(Figure7).
7).

Figure7.7.Batch
Figure BatchReactor
ReactorAssembly.
Assembly.

3.4.
3.4.Sample
SampleTreatment
Treatment
Batch
Batch reactorhaving
reactor having18 18cm
cmlength
lengthand
and3.3
3.3cm
cmwidth
widthshown
shownininFigure
Figure1,1,was
wasused usedtoto
carry
carryoutoutpyrolysis
pyrolysisexperiments.
experiments.Magnesium
Magnesium oxide catalyst
oxide was premixed
catalyst with commercial
was premixed with com-
waste
mercialtube rubber
waste tubepieces (5–8
rubber mm cross-section
pieces width). Catalyst
(5–8 mm cross-section width).toCatalyst
tube rubber
to tuberatio was
rubber
1:5 for was
experiment. The reactor was ◦ C in an automatic programmed
ratio 1:5 for experiment. The heated
reactor from
was 250–350
heated from 250–350 °C in an automatic
electric furnace,
programmed wherefurnace,
electric temperature
where was controlled was
temperature by a controlled
thermocouple.
by a After on hour
thermocouple.
of heating, glass tube was removed from the reactor and allowed to
After on hour of heating, glass tube was removed from the reactor and allowed cool down toto
room
cool
temperature. The pyrolysis products obtained were identified as gas, liquid
down to room temperature. The pyrolysis products obtained were identified as gas, (oil) and char
liq-
(solid).
uid (oil)The
andweight
char of these The
(solid). products was
weight ofmeasured accordingly
these products and product
was measured composition
accordingly and
was calculated
product via formula:
composition was calculated via formula:
Wt.Wt.of of
oiloil
% Oil ==
% Oil ××100
100 (1)
(1)
Wt.
Wt.of of
tube
tuberubber
rubber
Wt.
Wt. ofof residue
residue
Residue==
%%Residue × 100
× 100 (2)
(2)
Wt.
Wt. ofof tube
tube rubber
rubber
% Gas = % Conversion − (% Oil % Residue) (3)
The efficiency of the reaction was measured by percent conversion using the follow-
ing formula
(Wt. of tube rubber − Wt. of residue)
%Conversion = (4)
Wt. of tube rubber
Catalysts 2021, 11, 357 10 of 13

3.5. Distillation of Liquid from Catalytic Cracking of Tube Rubber

The distillation of oil obtained from catalytic conversion of tube rubber was carried
out in a standard 250 mL round bottom distillation flask attached to a distillation assembly
where, 100 mL sample oil was taken in a distillation flask and sample distillates were
collected and subjected to further analysis.

3.6. Physical Properties Analysis

Oil obtained (light and heavy oil) from catalytic cracking of tube rubber using mag-
nesium oxide as a catalyst at optimum conditions was analyzed to determine its physical
properties, such as density, viscosity, specific gravity, API gravity, kinematic measurement,
aniline point, flash point, diesel index, and Kw value via standard methods approved by
IP and ASTM.

3.6.1. Density
In typical standard experiment a specific gravity bottle (25 mL) was taken, washed,
cleaned and dried in an oven. The empty specific gravity bottle with lid was then weighed
using analytical balance. The bottle was filled with sample having no air bubble and
weighed again. The weight of sample was determined and its density was calculated by
the following relation:
D = M/V (5)
where, D = Density of sample, M = Mass of the sample, V = Volume of the sample

3.6.2. Specific Gravity

Specific gravity of the product oil was calculated using densities of oil and water via
following formula:
Density of Oil
Specific Gravity = (6)
Density of Water

3.6.3. API-Gravity
API-Gravity was calculated using following formula:

141.5
API − Gravity = − 131.5 (7)
Specific Gravity of sample oil

3.6.4. Viscosity
Following a standard method Ostwald viscometer was washed, cleaned and dried
in oven, where in a U-shaped glass tube was used to measure the time of flow of liquid
between to fixed marks. The experiment was repeated for water as well. Viscosity was
measured using the formula:

ή l d X tl
Viscosity = => l (8)
ή w dw X tw

where, ή l = Viscosity of sample oil, dl = Density of sample oil, tl = Time of flow of sample
oil, ή w = Viscosity of water, dw = Density of water, tw = Time of flow of water.

3.6.5. Kinematic Viscosity

Kinematic viscosity via standard method can be calculated using following formula:

ή l
Kinematic Viscosity = (9)
dl

where, ή l = Viscosity of sample oil, dl = Density of sample oil

Catalysts 2021, 11, 357 11 of 13

3.6.6. Aniline Point

The aniline point apparatus was washed, cleaned and dried. In outer tube (jacket tube)
paraffin was taken and in the inner tube equal volumes (10 mL of each) of sample liquid
and aniline was poured. The inner tube also had a thermometer and stirrer fitted in the
cork. Then heating was started slowly along with stirring until miscibility was achieved.
The temperature was noted at this stage. Then the content of the test tube was allowed to
cool. As soon as, the turbidity appeared, again the temperature was noted. Average of the
two temperatures was found out as aniline point of the sample liquid.

3.6.7. Flash Point

The cup was filled with sample and the meniscus was adjusted exactly at the filling
line. The sample cup was heated with heat and the temperature was initially raised at the
rate of 14–17 ◦ C per minute. The test flame was passed across the center of the cup until a
flash appeared on the surface of the oil. The temperature was recorded as the flash point.

3.7. Chemical Analysis

Chemical tests to determine the chemical properties of the oil obtained from the cat-
alytic cracking of tube rubber using magnesium oxide as a catalyst at optimum conditions
are as follows:

3.7.1. Qualitative Determination by Bromine Water Test

A known amount of 3 mL from liquid sample was mixed with 2 mL of 1% bromine
water solution in the presence of carbon tetrachloride. The solution colour got faint
immediately that indicated the presence of olefins in oil.

Potassium Permanganate Test:

An amount of 3 mL of liquid was mixed with 5 mL of 0.1% potassium permanganate
solution. The solution lost its color immediately which further confirmed the presence of
olefins as a major component in oil.

3.7.2. Quantitative Determination by Phenol Test using Antipyrene Method

Sample solution was prepared by mixing known volume of oil sample with 4% NaOH
solution (10 mL) and was shaken for 5 min. which later on was extracted and neutralized
with dilute hydrochloric acid. A buffer solution of pH = 10 (1 mL) was added to the sample
solution (10 mL) followed by the addition of 3% 4–aminoantipyrene solution (2 mL) and
6% potassium ferricyanide solution (8 mL). Final mixture was diluted up to 100 mL with
distilled water. The same procedure was applied to standards in the range of 0.05–3 ppm.
Absorbance for all working standards along with samples was measured at 510 nm
against blank.
From calibration plot, the concentration of phenol was determined in each sample.

3.8. Determination of Bromine Number by Mercury Catalyzed Bromate –Bromide Titration

A gram of heavy oil sample was taken in 250 mL volumetric flask. Then, 25 mL of
potassium bromate –potassium bromide solution and 20 mL of 10% sulphuric acid were
added to the falsk and was shaken for 5 min. To this mixture 10 mL of mercuric sulphate
was added and was mixed thoroughly, the mixture was allowed to stand for 7 min. Then
15 mL of 2 N sodium chloride solution was added followed by the addition of 20 mL
of 10% potassium iodide solution. The falsk was shake seconds liberating iodine which
was titrated against standard 0.1 N sodium thiosulphate solution. About 0.5 mL of starch
solution used as indicator to determine the end point. Bromine number was calculated
using the formula:

VKBrO3 KBr X N − VNa2 S2 O3 X N

Bromine Number for heavy oil = X 7.992 (10)
Wt. o f Sample
Catalysts 2021, 11, 357 12 of 13

4. Conclusions
Used tube rubber can advantageously be recycled via catalytic pyrolysis method. It
has been revealed that conversion of tube rubber in presence of MgO catalyst at lower
temperature into valuable liquid is a practicable procedure. Oil obtained from the catalytic
conversion of tube rubber at optimized conditions has shown resemblance to conventional
fuel, in terms of both physical as well as its chemical properties. Catalytic pyrolysis of
tube rubber is a useful recycling process from economic as well as environmental view
point. However, more in-depth studies are required to investigate these liquid fractions
separately. Furthermore, char obtained during the catalytic process may be a source of
activated carbon that can usefully be utilized in various processes such as wastewater
treatment. Here, it can be concluded that oils obtained from the catalytic conversion of
waste tube rubber might be developed as an alternative to conventional mineral oil.

Author Contributions: Author and all co-others have equally contributed in completion of this
work where project design, reaction reactor, assembly set up, methodology and investigation were
done by R.M.; software, M.N.U. and S.W.K.; manuscript writing, Y.A.; Statistics and data validation,
H.u.R.; manuscript writing and proof reading, A.R.; project administration, M.A.U.M.; funding
acquisition and expert opinion, Y.M. All authors have read and agreed to the published version of
the manuscript.
Funding: The APC was funded by University Laval (Project: CRSSNG).
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: The authors greatly acknowledge the guidance and technical support of Hendrik
Kosslick, Head of Material Design at Leibniz Institute for catalysis, University of Rostock Germany.
Conflicts of Interest: The authors declare no conflict of interest.

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