Review Article

Progress in Rubber Plastics and

Recycling Technology
Waste tires pyrolysis 1–15
ª The Author(s) 2019
oil as a source of energy: Article reuse guidelines:
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DOI: 10.1177/1477760619895026
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Vesislava Toteva and Kiril Stanulov

Abstract
A huge amount of waste tires is generated every day in the world. This determines the search for
ways to use them. The extended process of production and application of scrap tires leads to their
significant mass accumulation, thus representing environmental risk. Tires are inert materials,
extremely difficult to treat, and nonbiodegradable. In recent years, many plants have been built for
processing, treatment, and utilization of this kind of waste. A problem has emerged to find a
suitable, environmentally friendly application of the products (gaseous, liquid, and solid) from
pyrolysis of the tires. Pyrolysis oil, which is a liquid product, is not suitable for direct use as fuel
because of its high sulfur content. Therefore, the desulfurization of pyrolytic tire oil is an important
part of the oil production process prior to its use. The objective of this article is to review the
methods used for desulfurization of waste tire pyrolysis oils and the possibility of using scrap tires
as a source of energy.

Keywords
Recycling, pyrolysis, waste tires, fuel, desulfurization

Received 15 June 2019; accepted 30 September 2019

Introduction
Fossil fuel reserves are running out, and for decades, new sources of energy are being sought for.
These include fuels derived from alternative sources (raw materials) such as plant and animal fats,
waste biomass, polymers, and used tires.
Waste tires could be processed to liquid fuels and chemical reagents using the pyrolysis process,
which is a real alternative to their discarding into landfill or burial in the land. They have a

Department of Organic Synthesis and Fuels, University of Chemical Technology and Metallurgy, Sofia, Bulgaria

Corresponding author:
Vesislava Toteva, bul. “Sveti Kliment Ohridski” 8, 1756 Sofia, Bulgaria.
Email: vesislavatoteva@gmail.com
2 Progress in Rubber Plastics and Recycling Technology XX(X)

100
90

Recovery of waste tires, %

77.69 86.65
80
67.27
67.09
70 67.8
60
50
normative
40
30
goals achieved

20
10
65 65 65 65 65
0
2012 2013 2014 2015 2018
Year

Figure 1. Recovery of waste tires in Bulgaria.

significant part of the urban waste, and their quantity is steadily increasing. According to European
Tyre & Rubber Manufacturers’ Association,1 in the European Community, sales of new tires
increased in 2014 by 6% to 89.4 million units from 84.4 million. In Bulgaria, according to the
data of Executive Environment Agency,1 based on the quantity of tires purchased and the waste
tires, the achieved national recovery target in 2015 was 86.65% (Figure 1), with a normative set of
65%. In 2018, it dropped to about 68%.2 The national recycling and/or regeneration target achieved
in 2017 was 64.31% at a normative 35%. Figure 1 shows the goals achieved by recovery of waste
tires in Bulgaria.
Sienkiewicz et al.3 in their study concluded that material recycling and combustion of used tires
are currently the most technologically advanced methods of handling this waste in the European
Union. From an economic point of view, it is important to note that obtaining energy from
combustion of tires is more attractive than recycling. However, we get less energy from combus-
tion process of waste tires than we need for production of tires.

Waste tires recycling technologies

Various approaches are targeted to recycling the spent tires. Waste tires recycling technologies
include landfill, retreading, recycling (grinding and pulverization technology, devulcanization
technology), combustion, and conversion to liquid fuels (including gasification, hydrothermal
liquefaction, and pyrolysis).
Material recycling is realized as mechanical grinding of tires, which yields rubber materials of
different degrees of comminution or as devulcanization.3 Devulcanization is based on decom-
posing the cross-linked structure of vulcanized rubber. The devulcanized rubber can be revul-
canized into a raw material for rubber industry, which is a highly valued form of waste rubber.
The known methods of devulcanization include chemical, thermal, mechanical, and thermome-
chanical processes. They are improved by microwave irradiation.4 Nunes et al.5 use the extrusion
process that raises the efficiency of the thermomechanical recycling in the devulcanization of the
ground tire rubbers.
One of the main ways to recycle used tires or other waste rubber products is to use them as a fuel
referred to as tire-derived fuel (TDF). Used tires have a comparatively high caloric value, making
them competitive with other types of fuel, especially coal, which have much lower caloric value.
Toteva and Stanulov 3

The cement industry is one of the greatest consumers of shredded tires utilizing them as an
alternative fuel.
Another widely used method is pyrolysis, a process in which organic materials are thermally
decomposed into simpler compounds in the temperature range of 400–700 C in an oxygen-free
atmosphere, and Williams6 analyzed in detail this process for the recovery of waste from used tires
and obtained yields at 58.2 wt% for oil, 37.3 wt% for char, and 4.5 wt% for gas. Mui et al.7
reviewed the production of active carbons from waste tires. Experimental results of different
authors showed char yields from pyrolysis in the range of 33–42%. Under diverse activating
conditions, several active carbons with Brunauer, Emmett and Teller (BET) surface areas over
1000 m2/g have been produced with extensive micropore volumes. Pyrolysis of polymers is also
known as destructive distillation. Quek and Balasubramanian8 provide a critical review of past
efforts over the last four decades in oil and liquids production from the pyrolysis of waste tires. The
production of chemicals and other liquids, and oils in particular, by rubber pyrolysis has been
studied over the years under various conditions.
All types of vehicle tires can be subjected to pyrolysis, including motor, bicycle, rickshaws,
trucks, and tractors. Ucar et al.9 examine the polymers contained in tire from cars and trucks and
establish that the main components of truck waste tires are natural rubber (51%), butadiene–
styrene rubber (39%), and polybutadiene and butadiene rubber (10%), with small amounts of
organic and inorganic additives. Car tires contain about 35% natural rubber and butadiene about
65%. The other components of the tires are soot, oils that contain arenes, organic sulfuric com-
pounds, sulfur, zinc oxide, and stearic acid. Different variations of tire composition are possible
depending on the manufacturer, their quality, and purpose. Accordingly, Islam et al.,10 investigated
oils, gases, and char in relation to the pyrolysis of different brands of scrap automotive tires and
established that the composition of the products varied widely.

Chemical composition and types of sulfur compounds in liquid waste pyrolysis products
The composition of liquid products from waste tires pyrolysis is different but can be identified to a
great extent. Kyari et al.11 studied pyrolysis of seven different brands of used tires from several
countries and characterized the resulting liquid products. They found a considerable diversity in
the concentrations of the components of the liquid and gaseous products obtained. Cypres and
Bettens12 found a significant difference of about 10% in the yields of solid, liquid, and gaseous
products and examined the relationship and the correlation between the type of pyrolyzed tires, the
yield, and the composition (including the products obtained).
Pavlova et al.13 and Australian scientists Kan et al.14 have used gas chromatography–mass
spectrometry (GC-MS) for characterization of liquid products from pyrolysis of spent tires and
have established that pyrolysis liquids contain alkanes, cycloalkanes, and alkenes (C4–C12) as
well as arenes—predominantly alkylbenzenes and alkylnaphthalenes. Kan et al.14 show and com-
pare the chemical composition of pyrolysis liquids obtained from four types of feedstock—pneu-
matic tires, refractory synthetic, and two types of natural rubber. The results also show a variety of
aromatic, cyclic, and aliphatic hydrocarbons; benzene; 1-thiobenzoyl-2,4,6-trimethyl-(C16H16 S)
and compounds with different heteroatoms of sulfur and nitrogen; and small amounts of oxygen
compounds (about 10 peak area %: alcohols, cyclic esters, and their derivatives). Comparing the
tire materials under study, authors noted that the pyrolysis oils from pneumatic rubber tire con-
tained many more nitrogen-containing compounds (about 36 peak area %). In addition to the major
hydrocarbons, Islam et al.15 detected the percentage of nitrogen-containing compounds, sulfur, and
4 Progress in Rubber Plastics and Recycling Technology XX(X)

chlorine compounds. Oxygen-containing compounds in the form of acids are also present in the
resulting liquids. Stratiev et al.16, Laresgoti et al.17, and Pakdel et al.18 discussed that the most
abundant compound present in the pyrolytic liquids is isoprene dimer limonene and its content may
reach 30%.
To be used as a fuel, the sulfur content of liquid products should be reduced. According to Kan
et al.,14 sulfur compounds formation in the pyrolytic liquids is due to the thermal degradation of
additives such as vulcanization agents and accelerators added during the tire manufacturing pro-
cess. Sulfur is used as a cross-linking agent during the tire manufacturing process. According to
Quek and Balasubramanian,8 during pyrolysis, some sulfur heteroatom-containing compounds
form free radicals, and polythiyl radicals from polysulfide cross-linkages are thought to react by
addition to carbon–carbon double bonds, recombination, and/or disproportionation. The reaction
pathways change with the pyrolysis conditions (temperature, pressure, and residence time) and
yield different amounts of sulfur compounds in pyrolysis oil.
A number of researchers have studied the molecular structure of sulfur compounds that form the
total sulfur content. Using GC coupled with flame ionization detector, Jantaraksa et al.19 found that
sulfur compounds in pyrolysis oils are thiophenes, benzothiophenes, and dibenzothiophenes and
their derivatives. Scientists from Thailand, Saeng-arayakul and Jitkarnka,20 established that the
sulfur-containing molecules, found in the range of gasoline, kerosene, and gas–oil fractions of
pyrolysis oils, are benzothiophene derivatives such as 3-methylbenzothiophene (C9H8S), ben-
zo[b]thiophene, 2,5dimethyl-(C10H10S), and dibenzothiophene derivatives such as naphtho [2,3-
b] thiophene, 4,9-dimethyl-(C14H12S).
Pavlova et al.13 investigated the liquid product (boiling range of 35–200 C) produced from
spent tire and identified the following sulfur compounds: thiophene, 2-methyl thiophene, 2-[1-
methylethyl] ethyl mercaptan, and 1-(4-methoxymethyl) phenylbenzothiazole.
Benallal et al.21 investigated pyrolysis at 13 kPa and 500 C, the feed rate was 19 kg h1, and
they found that 1.2% of sulfur is in the pyrolysis oil as much as the raw material used. They also
found that sulfur compounds were mostly concentrated in light (the so-called gasoline fraction,
distilled up to 160 C) and were identified by GC-MS; the identified representatives of sulfur
compounds were as follows: 2-methylthiophene, 3-methylthiophene, 2-ethylthiophene, 2,5-
dimethylthiophene, 2,4-dimethylthiophene, 2,3-dimethylthiophene, 3-ethylthiophene, 2-
isopropylthiophene, 2-tert-butylthiophene, and benzothiazole.

Dependence of the type and amount of sulfur compounds on the reaction conditions of
pyrolysis
The composition of the sulfur compounds in the liquid products from waste tire pyrolysis is mostly
affected by the reaction conditions of the process. The mechanism of formation of the sulfur
compounds varies depending on the reactor temperature, rate of heating, type of reactor, treatment
time, and catalysts used.
Araki et al., using a fluidized bed reactor, found that the sulfur content of the pyrolysis obtained
was in the range of 1.35–1.46% and the temperature varied between 400 C and 550 C.22 Una-
pumnuk et al.23 examined the sulfur content of the product over a wider range of 350–1000 C.
They found that the influence of temperature is the highest in the range of 350–400 C: desulfur-
ization of the tires increases as temperature enhances from 350 C to 400 C but remains almost
constant above 400 C. The heating rate has no effect on the amount of sulfur. Similar results are
obtained by Dı́ez et al.24 who investigated the influence of temperature at three different values.
Toteva and Stanulov 5

They found elevated sulfur concentrations in pyrolytic fluids at the highest temperature (550 C)
due to the fact that higher temperatures favor the breaking of the C–S bonds in the original tire.
When using a fixed bed reactor, Teng et al.25 found that in pyrolysis products of used tires, 9%
of the sulfur in the tire is present in the pyrolysis oil, and most of the sulfur remains in the solid
product. The total sulfur concentration in the oil is only 0.3%. However, pyrolysis in this study is
for the purpose of producing activated carbon, not a liquid product, so the conditions are high
pressures and temperatures below 400 C. Williams et al.26 and Napoli et al.27 used reactors with a
fixed bed, in a stream of nitrogen and temperatures between 380 C and 720 C, in pyrolysis oils
sulfur varying from 1.1% to 2.2%. Under similar conditions, Roy et al.28 conducted the vacuum
pyrolysis of used tires for liquid products and sulfur in the range of 0.83–1.35%.
The sulfur polycyclic aromatic hydrocarbons (PAHs) in pyrolysis oils produced in fixed and
fluidized bed reactors at three heating rates to a final pyrolysis temperature of 700 C were
investigated by Williams and Bottrill.29 Dibenzothiophene and its alkyl derivatives have a signif-
icant increase in concentration when increasing the rate of heating. The concentrations of diben-
zothiophene and its alkyl derivatives in oil produced from a fluidized bed reactor show an increase
with increasing pyrolysis temperature. In particular, dibenzothiophene has shown a small change
with increasing pyrolysis temperature and its C2 and C3 derivatives increased significantly.
Mastral et al.30 conducted the coal–tire co-thermolysis in the presence of hydrogen (hydrogen
pressure 10 MPa) and three types of catalysts in the swept fixed bed reactor at temperatures of 400
and 450 C. The commercially available catalyst, Ni Mo/Al2O3, does not seem to work properly in
light fractions generation, cracking reactions, but it appears to be very efficient in heteroatoms
elimination.
Uçar et al.31 conducted co-pyrolysis of scrap tires with waste lubricant oil. Roy et al.32 and
Mirmiran et al.33 recycled waste tires to oil by vacuum pyrolysis at 500 CC, and sulfur content
varieties from 0.8% to 0.89%. Chaala and Roy34 established that raising the final temperature up to
520 C of the pyrolysis under vacuum leads to higher sulfur content of up to 1.5%. From the
available literature, the lowest sulfur liquid product (0.60%) is reported by Lopez et al.35 who
performed pyrolysis of granular tires in a pilot plant with a fixed bed reactor, and by a team of
Shah36 from Pakistan (0.55%) after pyrolysis in the presence of calcium carbide.
It is notable that the influence of the temperature and the heating rate is not unambiguous, and
the results obtained are contradictory. In all experiments carried out under vacuum and in the
presence of some catalysts, a product with a lower sulfur content is obtained.

Methods for desulfurization of liquid products obtained from pyrolysis of waste tires
The amounts of sulfur and, in many cases, nitrogen compounds in the fuels obtained from pyrolysis
of waste tires is even higher than in the fuels distilled from crude oil. The presence of heteroatoms
in the composition can result in an incomparably great negative environmental effect in case of the
formation of highly toxic compounds in the process of combustion. Problems caused by nitrogen-
containing compounds include gum formation, acid catalyst inhibition and deactivation, acid–
based pair-related corrosion, and metal complexation. However, no evidence has been found of
studies conducted in the field of denitrogenation of pyrolysis oils, indicating that the efforts of the
researchers should be directed in this way.
As desulfurization of pyrolytic tire oils is an important part of the oil production process before
it can be utilized, there are a number of studies on this topic.
6 Progress in Rubber Plastics and Recycling Technology XX(X)

Hydrodesulfurization. The conventional industrial process used to remove the sulfur compounds
from the petroleum fractions is the hydrodesulfurization (HDS) in which the raw material is
heated, mixed with hydrogen in a reactor with the catalyst. The reactor temperature is between
300 C and 390 C. The pressure varies from 1.5 MPa to 9.0 MPa, depending on the type of sulfur
compounds and whether they are difficult to remove.
Very few studies have been carried out in the field of desulfurization of waste tires pyrolysis oil
(WTPO) by HDS. Jantaraksa et al.19 reduced the sulfur content of liquid product from tire pyr-
olysis by HDS catalyzed by molybdenum (Mo), nickel-Mo (NiMo) or cobalt-Mo supported on
alumina (g-Al2O3). The influence of the catalyst nature, the level of filling, hydrogen pressure,
temperature, and reaction time was studied. For every catalyst, the maximum percent sulfur
removal (87.8%) was achieved when the reaction was performed at 250 C for 30 min using a
2-wt% NiMo/g-Al2O3 catalyst, loading based on the WTPO content and 20 bar initial hydrogen
pressure. The resulting fuel cannot replace the conventional since it does not fully comply with the
quality specifications.
Tsaneva et al.37 explored four different ways of desulfurization of a WTPO: (1) Fractionation to
light (gasoline fraction) and heavy pyrolytic oils (POs) and two-stage hydrotreatment of the
gasoline fraction; (2) Hydrotreatment of a blend of the whole PO with straight run diesel fraction
from the Russian Export Blend Crude Oil (REBCO); (3) processing of the whole PO along with
REBCO in a crude distillation unit; and (4) direct blending of the whole PO with a commodity fuel
oil. It was found that in the fractionation of liquid pyrolysis in two fractions—mild and heavy—the
heavy fraction corresponds to the specification of fuel oil and marine fuel. The light fraction is
hydrotreated in a laboratory hydrotreating reactor. The product contains less than 10 ppm of sulfur
and has an octane number of RON ¼ 88.9 and MON ¼ 77.0. The results of HDS of a blend of PO
with Russian crude oil (REBCO) have shown that PO inhibits mononuclear aromatics hydrogena-
tion when its content in the mixture is raised up to 20%. The addition of the PO to the crude oil
REBCO improved the yields of distillates in the laboratory atmospheric-vacuum distillation unit,
but the quality of the distillates deteriorated, due to the chemical instability of the WTPO compo-
nents. It is possible to produce the fuel oil by blending not more than 3% of PO to a commodity fuel
oil whose closed cup flash point is not lower than 86 C.

Alternative methods for desulfurization of liquid pyrolysis fraction from used automobile tires. The com-
panies that process waste tires through pyrolysis generally do not have the capacity to remove
sulfur, such as large refineries, and have problems supplying hydrogen. There are technologies for
desulfurization that do not use hydrogen for catalytic decomposition of sulfur compounds—they
are easy available and they can achieve high levels of sulfur removal.
Among the existing alternatives to HDS methods, described in the review papers of Babich and
Moujin38 and Al-Lal et al.,39 the following methods could be emphasized (Figure 2):

a. Desulfurization by extraction: The sulfur compounds are more soluble than hydrocarbons in
polar solvents. This method requires low temperature and low pressure, therefore can be
performed under ambient conditions. In US patents, acetone, ethanol, methanol,40 poly-
ethylene glycol,41 acetonitrile, and DMF are used.42 These solvents have shown high levels
of desulfurization, reaching between 50% and 90% of the sulfur removal.
b. Oxidative desulfurization and extraction: Blend the fuel with an oxidant (e.g. hydrogen
peroxide (H2O2) and acetic acid) at temperatures below 100 C and at atmospheric pressure,
the reaction product is extracted with a polar solvent such as those mentioned above.
Toteva and Stanulov 7

HDS: T=120-400 oC,

Catalysts: Mo/, NiMo/ or CoMo/ɣ-
Al2O3
Sulphur Reduction 87,8 %
Exrtaction with solvents:
mathanol, ACN, distilled
water

Additives: CaO, ODS: H2O2, catalysts:

Ca(OH)2, Waste tires oil organic acids, Fenton,
zeolite, NaOH desulphurization transiton metals,
ultrasound assisted

Adsorption
with SiO2, pyrolysis char
Acid purification
(H2SO4, HCl, HNO3)
Sulphur Reduction 35 - 84 %

Figure 2. Methods for desulfurization of waste tire pyrolysis oils.

Toteva et al.43–45 have combined oxidation and extraction procedure that has yielded
excellent results in laboratory experiments as well as improved other specifications such
as cetane number, density, and aromatic content. Mokhtar et al. have made optimization of
oxidative desulfurization of Malaysian Euro diesel fuel utilizing tert–butyl hydroperoxide–
dimethylformamide system.46 Taha et al. conducted oxidative desulfurization of diben-
zothiophene from model oil using ionic liquids as extracting agent.47 Bakar et al. investi-
gated the effect of transition metal oxide catalysts on oxidative desulfurization of model
diesel.48 Some of these combined methods are applied in industrial or pilot plants:
UniPure process49 uses H2O2 and organic acid catalyst as an oxidizer; Lyondell Chemicals
technology50 oxidizes with t-butylhydroperoxide and uses extraction to remove sulfones;
“SulphCo” applies ultrasonic oxidation technology.51
c. Adsorptive desulfurization: This method is based on the use of a solid adsorbent for the
selective adsorption of sulfur compounds, either by physical adsorption (adsorptive desul-
furization) or by a chemical reaction between the sulfur compounds in the fuel, as the
adsorbent usually forms sulfides (chemical adsorption). Kim et al. provided ultradeep
desulfurization and denitrogenation of diesel fuel by selective adsorbtion over three differ-
ent adsorbents.52 Wang et al. reported that via coupling adsorption with an oxidation
reaction, the total sulfur content of commercial fuels was dropped to below 15 ppm.53
d. Eterigho and Olutoye54 have conducted sulfuric acid treatment for improving the quality of
liquid fuels. They point out sulfuric acid treatment as the most economical and effective
method for removal of impurities from petroleum products among the various purification
techniques.

ODS of WTPO. Oxidation desulfurization (ODS) studies of WTPO are based on the results of ODS
of petroleum fractions, which show that the efficiency of the process is achieved by the use of H2O2
and organic acids as catalysts. An example of this is the study of Ramirez-Verduzco et al.; the
oxidation was carried out with a mixture of H2O2 and acetic acid as catalyst. The extraction of the
8 Progress in Rubber Plastics and Recycling Technology XX(X)

corresponding sulfones was performed with polar solvents.55 Dehkordi et al.56 also reported ODS
of non-hydrotreated kerosene using H2O2 and acetic acid. In other studies, the catalysts for ODS
contained transition metals: Zhou et al.57 have used MoO3. Shiriashi et al. used titanium silicate
molecular sieve catalysts58 or provided the photochemical desulfurization.59 An ultrasound-
assisted oxidative desulfurization was done by Mei et al.60
Al-Lal et al.39 removed sulfur compounds in a pyrolysis fraction by oxidative desulfurization
with H2O2 and extracting the polar oxygenated sulfur compounds in two ways: by extraction with a
polar solvent such as methanol or by adsorption with silica. Oxidation is optimized using Fenton
catalysts, ultrasound and irradiation, as recommended in ODS studies of petroleum fractions of Dai
et al.,61 Bhasarkar et al.,62 Duarte et al.,63 and Flores et al.64 These methods significantly reduce the
sulfur content of gas oil or diesel fractions, but in this case, the investigated waste product pyrolysis
fractions have high sulfur content and also contain high amount of olefins and arenes.
A team of Spanish scientists39 have tested two different desulfurization procedures, both based
on oxidation of sulfur compounds (oxidation with peroxiformic acid and H2O2/Fenton catalysts),
followed by extraction of more polar oxidized sulfur compounds, either by methanol or by silica
gel column adsorption. The procedure described in this work could allow the pyrolysis fuels from
waste materials to be blended with another waste origin material like animal fat biodiesel. Desul-
furization rate by 87.5% was achieved. For comparison, Dai et al.61 have found that ODS of the
diesel fuels catalyzed by FeCl3 leads to a reduction of 70% in sulfur content.
Scientists from South Africa, Tsietsi et al.65 have applied the method of gas–liquid oxidation
adsorption. They have established that in gas-phase adsorption by iron and molecular sieves, the
total sulfur removal is 19.6%. The sharp odor of the fraction also decreases, which is explained by
the mercaptans and sulfides being cleared when the moisture is removed from the fuel. The high-
molecular-weight sulfur compounds are purified using liquid-phase adsorption on activated car-
bon. The scientists observed the formation of a fibrous structure in the pyrolysis fraction (final
boiling point 300 C). It is probably formed as a result of the oxidation of fuel leading to the
formation of asphaltenes. Ultrafine particles are bonded from these fibers and can be filtered.
Chen et al.66 apply oxidative desulfurization of pyrolysis oil assisted by ultrasound. The oils are
mixed with tetra-octylammonium bromide (phase transformation agent) and a H2O2 solution
containing phosphotungstic acid (H3PW12O40, a transition metal catalyst). The oils in the mixture
are then oxidized by ultrasonic emission with frequency of 20 kHz for 20 min at 88 C. The oils are
then extracted with acetonitrile. Using this process, removal of a maximum of 43.6% of the sulfur
content of the pyrolysis oil has been achieved. By combining this ultrasonically assisted oxidation
process with subsequent adsorption with aluminum oxide, the desulfurization rate increased to
68.2%. It was found that the degree of desulfurization is affected by the amount of transition metal
in the oxidation catalyst, the duration of sonication, the diameter of the adsorption column, and that
an optimal result (89% desulfurization) is achieved after two-stage ultrasound-assisted ODS with
subsequent adsorption by Al2O3.
Trongkaew et al.67 conducted photocatalytic desulfurization of pyrolysis oil from waste tires.
The effect of the amount of TiO2 (1–10 g L1), also of the photoreaction temperature (30–70 C),
the proportion and type of the oxidant, and the extracting solvents, on the degree of desulfuriza-
tion rate were investigated. Distilled water, methanol, or acetonitrile was used as extraction
solvents. Water is added to methanol or acetonitrile to remove oxidized sulfur compounds from
the hydrocarbon pyrolysis fuel fraction. It was found that the maximum sulfur removal rate of the
pyrolysis oil was 43.6%. The conversion of sulfur compounds into PO is monitored by GC-FPD
Toteva and Stanulov 9

and high-performance liquid chromatography. The results show that the pyrolysis oil contains
sulfur compounds consisting of large molecular structures and that photo-oxidized sulfur com-
pounds have a higher polarity which helps for their easy separation from the oil by pyrolysis
using distilled water as solvent. Some researchers68 have been monitoring the change in sulfur
oxides SOx in the exhaust gases when burning the pyrolysis oil desulfurized by ODS. Besides
them, they also explore gaseous emissions (O2, CO, NOx, and CO2) using flue gas analyzer.
In both publications,66,67 it is reported that, using photocatalytic, ODS did not achieve such a
high degree of desulfurization as with the ultrasound-assisted method, but due to the different
starting sulfur content of the raw materials and different fractional composition, explicit conclu-
sions cannot be made.

Acid purification. Dogan et al.69 combined traditional sulfur acid (H2SO4) purification with the ODS
in a five-step process: (1) treatment with H2SO4, (2) treatment with activated bentonite—calcium
oxide (CaO), (3) vacuum distillation, (4) oxidative desulfurization, and (5) washing and drying.
The crude pyrolysis oil is mixed with 8% mass sulfuric acid for 4 h at 50 C. The mixture is divided
into a clear, viscous, oily layer at the top and at the bottom—nonviscous acid precipitate. The upper
oil layer is then stirred with activated bentonite and calcium oxide for 4 h at 70 C. After filtering
through a fabric filter, the filtrate was subjected to vacuum distillation. The distilled pyrolysis oil is
then treated with a mixture of formic acid and H2O2, stirred for 2 h at 60 C during the oxidation
desorption stage. The clear pyrolysis oil was then separated (through a separating funnel) and
washed with distilled water and dried at 110 C for 30 min. The purified pyrolysis oil contains
0.43% sulfur and 1% carbon residue, compared to 1.13% sulfur and 21.5% carbon residue in crude
pyrolysis oil.69 It also has a lower heating value of 40 MJ kg1 and can be used as a fuel. The study
concludes that compounding diesel with 30–70% of desulfurized pyrolysis oil from tires can be
used in diesel engines, without significant loss of engine functionality, while improving some
engine emission parameters.
In the review paper of Ahmad and Ahmad,70 it was noted that large number of researchers use
acids, mainly H2SO4, as a way to reduce the sulfur content of pyrolysis oils. Researchers from
Bangladesh—Islam and Nahian71—apply a methodology in which the process passes through
three stages: drying, treating with H2SO4 and distillation. The sulfur is reduced from 1.12 to
0.43 mass%. The desulfurization phase lasts too long—40 h, and the use of the extract containing
acid and sulfur compounds causes potential problems. Sulfur-based pyrolysis oil is blended with
diesel fuel in varying ratios and, after experiments, it has been found that a blend of 25% pyrolysis
oil and 75% diesel can be used without engine modification.
Aydın and Ilkılıç72 initially investigated the effect of pyrolysis temperature and additives on the
sulfur content of pyrolysis oils. Authors found that differences of about 0.3 wt% lower sulfur
content could be found for an oil produced at 550 C compared to a tire pyrolysis oil produced at
400 C. To reduce the sulfur content of a liquid pyrolysis product, they use catalysts NaOH,
Ca(OH)2, and calcium oxide (CaO-lime) during the pyrolysis process. Optimal results are achieved
with Ca(OH)2 and CaO. It is established that sulfur content is 34.25% lower using 5% Ca(OH)2 in
the reaction.
In the next step, these researchers72 used H2SO4 for desulfurization and found that the optimal
amount is 10%: sulfur decreases by 75%—from 1% to about 0.2%. Thus, with 5% Ca(OH)2 and
then with 10% H2SO4, the sulfur content of the product is reduced with about 84%. Also, the
authors use mixture of acetic or formic acid with H2O2. It has been found that, in a ratio of 2:1
10 Progress in Rubber Plastics and Recycling Technology XX(X)

acetic or formic acids to pyrolysis, oil mixtures are more effective than 1:1 molar ratio, but the
results are worse than using 10% H2SO4.
A similar approach was used by Ahmad et al.73 They have conducted experiments on desulfur-
ization of pyrolysis liquid products with H2SO4, H2O2-CH3COOH mixture (1:2 molar ratios),
bentonite, or CaO. The latter are added in amounts of 5, 10, and 15% by weight, respectively.
The sulfur content of the pyrolysis oils decreases as the amount of H2SO4 increases. Maximum
desulfurization rate of 35% using H2SO4 is achieved by treatment with 15 wt%, corresponding to
0.63 wt% sulfur in purified oils. The sulfur content is most effectively reduced by the oxidation-
catalyst mixture H2O2-CH3COOH; the best result is obtained for desulfurization of 50% corre-
sponding to 0.5 wt% sulfur. The advantages of the process are low temperature (50 C) and short
reaction time (1 h). Regarding the removal of sulfur from pyrolysis oils by Fuller’s earth, it should
be noted that, in this case, the poorest results are achieved, and when using CaO, a 20% degree of
purification is accomplished, which corresponds to 0.77 wt% of sulfur. Bentonite and other natural
adsorbents can be used as deodorizing and decolorizing agents. The authors recommend that, after
oxidative desulfurization, extraction or adsorption purification is applied.
Research teams from Thailand, Rujiravorawut et al.,74 besides H2SO4, for desensitization also
used both nitric acid (HNO3) and hydrochloric acid and compared the results of the parallel
experiments. They showed that the yield of the purified pyrolysis oils with H2SO4 and HNO3 is
about 50% by weight. With hydrochloric acid, the yield is reduced by about 10% by weight. The
resulting oils contain 5% gasoline, 25% kerosene, 35% gas oil, 8% light vacuum gas oil and 27%
heavy vacuum gas oil. The results of two-dimensional gas chromatography with time-of-flight
mass spectrometer (GC  GC-TOF/MS) show that purification with conventional strong acids
such as H2SO4, HNO3, and hydrochloric is not suitable for improving the quality of pyrolysis oils
from tires, due to the presence of acidic residues, containing polyaromatic and sulfur compounds
with high concentration.

Use of the solid residue from tire pyrolysis as a desulfurization adsorbent. Bunthid et al.75 desulfurized a
fraction of low octane gasoline, distilled from light fractions derived from tire pyrolysis. They
found that the maximum degree of desulfurization was 41.5% and 47.6%, respectively, using only
H2O2 or an adsorbent solid residue from tire pyrolysis. Upon application of oxidation and adsorp-
tion, by simultaneous use of H2O2 and a solid pyrolysis residue of tires, the degree of desulfuriza-
tion increases up to 57.8%.
The highest degree of desulfurization, up to 75%, is achieved with the use of HNO3-modified
charcoal (pH 4 aqueous medium regulated by formic acid). The surface treatment of pyrolysis
char by HNO3 and H2O2 has increased the sulfur removal capacity due to the decrease in
deposited sulfur and the increase in the surface density of oxygenated functional groups on the
char surface.
Uçar et al.76 increase the quality of PO from heavy-duty tires using Co-Ni, Co-Mo, and Ni-Mo
catalysts deposited on a carbon black at 350 C and a hydrogen pressure of 7 MPa. All three
metal-containing catalysts can reduce the sulfur content from the initial 0.77% to 0.57% (Ni-Mo
catalyst). Ni-Mo catalysts also provide a maximum yield of 55% low octane gasoline (boiling
temperature <172 C), 20% kerosene (boiling temperature 172–232 C) and 25% vacuum gas oil
(boiling point >232 C), with 17.7% arenes, 81.1% alkanes, and 1.25% alkenes. The results from
experiments with a commercial catalyst containing nonprecious metals on a silica-g-Al2O3
support were not good.
Toteva and Stanulov 11

Conclusions
The processing of waste tires by pyrolysis is a promising method of using this type of widespread
waste product. The liquid product of the process has properties close to those of petroleum fuels,
but high sulfur content is a problem for its direct use. Sulfur compounds are found to be similar in
pyrolytic and petroleum fuels: they are predominantly derivatives of thiophene, benzothiophene,
and dibenzothiophene. The chemical composition of WTPO, including the types of sulfur com-
pounds is significantly influenced by the technological factors: temperature, pressure, catalysts,
type of pyrolysis reactors, but whatever optimization is used, the quantity of sulfur in the final
product that exceeds the requirements of the fuel standards.
Conventional HDS is an expensive process and a large amount of hydrogen is required to
achieve low sulfur levels in pyrolysis oil. Therefore, the attention of the researchers is focused
on alternative and accompanying HDS methods. Acid purification is not promising because of the
presence of waste acid residues with high concentration of sulfur compounds and polyaromatic
hydrocarbons, which in turn presents an environmental problem.
Oxidative desulfurization is a reliable method for both petroleum and pyrolytic fluids. In com-
bination with extraction or adsorption, it could effectively remove the refractive sulfur compounds to
low levels, then through HDS, to achieve ultralow sulfur level or use directly as industrial fuel.

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.

Funding
The author(s) received no financial support for the research, authorship, and/or publication of this article.

ORCID iD
Vesislava Toteva https://orcid.org/0000-0002-5366-8798

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