INTRODUCTION .

1
With the rapid development of the automobile industry, about 1.4 billion used tires
were regarded over the world annually.1 It was predicted that the number of waste
tires (WTs) would exceed 1.6 billion in 2024,2 and the increase would reach 20% by
2030.3 Various economic and environmental problems were aggravated due to the
increasing quantity of WTs and inappropriate recycling methods in the long term.4−7
Therefore, it is significant for WT disposal to explore effective, profitable, and
environmentally friendly methods. Pyrolysis was considered the most prevalent,
attractive, and environmentally friendly among WT thermal conversion technologies
owing to the advantages of faster reduction, less environmental pollution, and higher
economic benefits.2,8−11 However, there were some shortcomings of pyrolysis
products. For tire pyrolytic oil (TPO), drawbacks of high sulfur content and viscosity,
low flash point and cetane number, and impurity restricted its direct utilization.12−17
With regard to pyrolytic carbon black (CBp), it was possible to be used as reinforcing
filler and pigment in rubber and the precursor of activated carbon.18,19 Nevertheless,
CBp’s intrinsic drawbacks, including high ash and sulfur content, poor micropore
structure, and carbonaceous residues on the surface, still hindered its direct
utilization.1,20,21 As mentioned above, to improve the economic performance of
pyrolysis process, the upgrading of TPO and CBp was necessary. To obtain the clean
liquid products, the researchers actively developed the different desulfurization
methods of TPO, including in situ and ex situ desulfurization. In situ desulfurization
referred to the direct removal of organic sulfur in TPO through additives during the
pyrolysis (such as NaOH, Ca(OH)2, Na2CO3, CaO, and zeolite).22−26 Generally, the
in situ desulfurization efficiency was not ideal. Meanwhile, it was difficult for
additives to separate from the pyrolytic solid product. By contrast, ex situ
desulfurization was more effective than in situ desulfurization but more expensive
owing to additional desulfurization equipment.27 Hydrodesulfurization (HDS) was a
traditional method of ex situ desulfurization, and the most commonly used to fulfill
the sulfur removal of oil products. The experimental results of HDS under different
catalysts and parameters demonstrated that the maximum removal efficiency could
reach 99.9%.28,29 Different from sulfides without ring structure, dibenzothiophene
(DBT) and substituted DBTs were more difficult to be removed through HDS owing
to the influence of steric resistance.29,30 Despite all this, other methods of ex situ
desulfurization were unable to achieve the same efficiency as HDS, although some
disadvantages of HDS could be eliminated.31,32
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Gaining in popularity is pyrolysis which would convert waste tyres into valuable
chemicals and/or alternative fuels for compression ignition engines (Hita,
Arabiourrutia, Olazar et al. 2016). South African is currently bedevilled by an energy
crisis with the power outage first witnessed in 2007 becoming a permanent feature
and pose a serious threat to the much needed economic growth. Therefore, the
growing commitment to and investment in the development of innovative
technologies for waste tyres recycling and processing in South is impelled by
environmental as well as economic factors. The unsustainability and the public health
concern of the present landfilling disposal method and the country dependency on
imported crude to meet the growing demands for transportation fuels and energy has
led to the growing investment in the development of commercial processes for the
conversion of scrap tyres to fuels and energy in South Africa. 4 The Integrated
Industry Waste Management Plan (IIWMP) approved on 28 November 2011 among
others created the Recycling and Economic Development Initiative of South Africa
(REDISA), an organization charged to implement the plans set out in the IIWMP and
is expected to develop a sustainable South African tyre recycling and processing
industry. New regulations are being implemented in South Africa by REDISA in
conjunction with the Department of Environmental Affairs to curb illegal dumping of
waste tyres. The regulations dictate that all tyre manufacturers and importers must
register and pay a levy for every kilogram tyre brought into circulation. These funds
will then be allocated to the collection and safe disposal of the waste tyres. Another
portion of the funds will be used for research and development purposes to create
recycling processes to solve the dilemma (REDISA 2013). It was realised that waste
tyres can serve a source of fuels and chemicals. By taking this approach, waste tyres
to fuel process may be employed to develop sustainable energy processes which have
the added benefit of job creation in the South African economy. In order to achieve
the goals set out in the IIWMP with respect to the development of homegrown
technologies and expertise in the management of waste tyres, it is necessary to
develop processes, technologies and expertise in waste tyre processing. Current
efforts are geared towards using this hitherto waste for the production of fuels,
chemicals and innovative products. The main challenge is to develop innovative
technologies for the production of fuels for transportation, agricultural machineries
and industrial (heating) applications that are economically viable on a large scale.
Such technology must be suitable for the South African environment, and provide
opportunities for human capital development through skills development and
technology transfer and ultimately facilitate job opportunities and wealth creations.
Hence the plant must be cost effective, energy efficient and with minimal
.environmental footprints
Hita, I., Arabiourrutia, M., Olazar, M., Bilbao, J., Arandes, J. M. and Castaño, P.
(2016) Opportunities and Barriers for Producing High Quality Fuels from the
.Pyrolysis of Scrap Tires. Renewable and Sustainable Energy Reviews 56: 745-759
REDISA (2013) Recycling and Economic Development Initiative of South Africa
Recycling and Economic Development Initiative of South Africa, acesssed 27 May
./2013 from http://www.redisa.org.za
Waste Tyre Recycling Methods
There exist numerous types of disposal routes for waste tyres. Some are
environmentally friendly and safe with the benefit of energy recovery when processed
in the correct context while others are impacting our daily lives in an adverse way. In
Europe, ELT recovery and treatment have taken center stage by setting a target of
95% recycle/recovery by 2015. Figure 2shows the improvement of waste tyre
management and utilization as of 2010 (European Tyre & Rubber manufacturers'
.association 2011)

Waste Tyres as Fuels

Due to the fact that waste tyres have a much higher calorific value than coal it is
possible to use tyre as a fuel substitute. (İlkiliç and Aydın 2011). Cement plants being
energy intensive are the main consumers of Tyre-derived Fuels (TDFs). Other
industries making use of TDFs are thermal power stations and the paper and pulp
industries. Advantages of using TDFs include cheaper stock costs than coal and
significantly reduced CO2 emissions, thus it provides savings on carbon taxes
.(Portland Cement Association 2008)
Retreading of Worn-out Tyres
Retreading, recapping or remolding is a process of increasing the life span of a worn
tyre. The process involves the removing of the old tread by high speed mechanical
buffeting (The Tire Retread & Repair Information Bureau 2013). Once clean the new
tread can be applied to the casing by Mold Cure or Pre Cure methods. Retreading
tyres consumes twothirds less energy and releases one third less greenhouse gasses
compared to the production of new tyres making it both an economical and
environmentally friendly option of recycling tyres (The Tire Retread & Repair
Information Bureau 2013). 6
Materials Recovery
Once retreading is no longer a possible option to recycle tyres, material recovery is
sought. Tyres are mechanically separated into their rubber, steel and textile parts as
far possible. The steel and textile can be recycled while the rubber is shredded or
powderized depending on the final application. The rubber is used extensively for
civil engineering applications and can be moulded into new rubber products such as
dustbins, furniture, wheelbarrows etc. An added advantage of material recover is that
the physical volume of the tyre that cannot be used and needs to be discarded is
.reduced by a factor of four (ChemRisk LLC 2009)

Thermo-chemical Conversion

Waste tyres with a gross calorific value of 3.3 ×104 kJ/kg similar to that of coal, cheaper cost
compare to fossil fuels and reduced CO2 emission has attracted interest as feedstock in
Wastes-to-Energy (WTE) plants. The high energy content is recovered for instance via
thermo-chemical conversion process as fuels and chemicals. Pyrolysis the thermal distillation
or decomposition of organic matters into oils, gases, and char (Kordoghli, Paraschiv,
Tazerout et al. 2015), is receiving the most attention as a way of converting the waste tyre
into fuels. The decomposition occurs by the application of heat in the absence of oxygen, or
under conditions where the oxygen concentration is too low for combustion or gasification
.reactions to occur (Zabaniotou, Antoniou and Bruton 2014)

The resulting products are liquid hydrocarbon fuels, combustible non-condensable gases at
atmospheric conditions) and solid char remains mostly comprising of carbon black. The
products distribution depends on the reaction conditions including temperature, pressure,
space time, the heating, use of catalysts and so on (Choi, Jung, Oh et al. 2014, Hu, Fang, Liu
et al. 2014, Raj, Kennedy and Pillai 2013, Williams 2013). Figure 3 shows a simplified diagram
.of the pyrolysis of waste tyres (Martínez, Puy, Murillo et al. 2013)
Pyrolysis oils can be used directly or as a blend with other heavy oils for industrial
heating or as feedstock in petrochemical processes. It can as well be upgraded into
transportation 8 fuels by lowering the sulphur content to acceptable level using
conventional refining process. The non-condensable gases on the other hand can be
used as fuel gas or electricity generation. Further processing using conventional
refining processes (for instance hydrotreating for sulphur removal) can produce diesel
ranges fractions suitable as transportation fuels and chemicals as feedstock for
.petrochemical processes
Despite extensive research efforts, the expected wide spread application of pyrolysis
on a commercial scale is still being hampered by economics majorly due to the cost
associated with improving the products comparatively low quality as well as the
process high energy demand. To be widely marketable the sulphur and other
impurities present in the oils and gas stream must be lowered requiring added unit
operation. There is also the issue of the gaseous pollutants emission from the plant.
Thus in order to make waste tyre pyrolysis an attractive alternate, a robust design is
needed to deal with all these factors. Most studies focus on the optimization of certain
process parameters that target specific products or yields of waste tyre pyrolysis with
.little emphasis on commercial viability and large scale operation
Current research into waste tyre pyrolysis seeks to maximize oil yield while changing
different process conditions, reactor set-ups, catalysts and heating units such as
microwaves and open flames. However, during waste tyre pyrolysis a vast range of
process variables have been identified to affect both the product yields and quality to
.varying degrees

Aims and Objectives of the Research

The main thrust of this project is to investigate the mechanism of thermal degradation of
waste tyres as influenced by the chemical composition in order to identify factors that
influences the products distribution from waste tyre pyrolysis. These include hydrocarbon
gases and oil and other recoverable materials, particularly the carbon black. To realise this
,aim, the study focus on the following objectives

a) Analysis of waste tyres chemical compositions to develop a model to predict the

.elemental composition of waste tyres from proximate analyse

b) Preliminary investigation into the mechanism of thermal degradation of waste tyres

which influences the pyrolytic process conditions and oil yield to develop reaction rate
.kinetics

c) Determine the production distributions as a function of process conditions in terms of

liquid products yields

d) To analyse the chemical compositions of the oil and recoverable materials from the
pyrolysis reaction to determine appropriate end use and applications and/or unit operations
required for its upgrading
Scope of Study

Various forms of pyrolysis processes have previously been investigated such microwave,
catalytic and co-pyrolysis process to produce transportation fuel grade hydrocarbons from
scrap tyres. In this study the focus is on the analyses of the liquid hydrocarbons in the
pyrolytic oil using an inductor furnace for the pyrolysis of scrap tyres. The intention is to
.improve on the yield of C5+ hydrocarbons while minimizing the pyrolytic gases formation

European Tyre & Rubber manufacturers' association (2011) End of Life Tyres: A Valuable
.Resource with Growing Potential: 22

İlkiliç, C. and Aydin, H. (2011) Fuel Production from Waste Vehicle Tires by Catalytic Pyrolysis
.and Its Application in a Diesel Engine. Fuel Processing Technology 92: 1129- 1135

Portland Cement Association (2008) Portland Cement Association Sustainable Manufacturing

.Fact Sheet. Association, P. C

The Tire Retread & Repair Information Bureau (2013) A Beginner's Guide to Retreading The
.Tire Retread & Repair Information Bureau, acesssed February 13, 2014

.ChemRisk LLC (2009) Tyre Generic Exposure Scenario. End of Life Tyre Guidance

Kordoghli, S., Paraschiv, M., Tazerout, M. and Zagrouba, F. (2015) Waste Tyres Pyrolysis:
Managing the Environmental Hazards of Scrap Tyres. Proceeding of 2015 6th International
Renewable Energy Congress (IREC), Sousse, Tunisia 24-26 March 2015, Institute of Electrical
and Electronics Engineers, pp 1-6

Zabaniotou, A., Antoniou, N. and Bruton, G. (2014) Analysis of Good Practices, Barriers and
.Drivers for Elts Pyrolysis Industrial Application. Waste Management 34(11): 2335- 2346

Choi, G.-G., Jung, S.-H., Oh, S.-J. and Kim, J.-S. (2014) Total Utilization of Waste Tire Rubber
through Pyrolysis to Obtain Oils and Co2 Activation of Pyrolysis Char. Fuel Processing
.Technology 123(0): 57-64

Martínez, J. D., Puy, N., Murillo, R., García, T., Navarro, M. V. and Mastral, A. M. (2013)
.Waste Tyre Pyrolysis - a Review. Renewable and Sustainable Engergy Reviews
A typical tire may contain up to 30 different types of synthetic rubber, 8 different natural
rubbers, in addition to a range of different carbon black fillers and up to 40 different additive
chemicals. The main rubber types used are, typically, styrene– butadiene-rubber, natural
rubber (poly-isoprene), and poly-butadiene rubber [3]. Apart from energy and carbon
material production, a wide range of materials which are illustrated in Table 1 can be
.recovered

Researchers concluded that yields of oil, gas, and char were not significantly influenced by
the type and origin of the tire. However, there were noticeable differences in the
.composition of the derived gases and oils [3]

P. T. Williams, "Pyrolysis of Waste Tyres: A Review," Waste Management, vol. 33, no. 8, ]3[
.pp. 1714-1728, 2013

A. Evans and R. Evans, "The Composition of a Tire:Typical Components," The ]7[

Waste & Resources Action Programme, Banbury, 2006
.Pyrolysis .

Pyrolysis is an endothermic process, an environmentally attractive method for the

treatment of tire wastes. The process uses medium temperatures (300 - 700) oC and an
oxygen-free environment to decompose solid tire wastes chemically in to char, oil, and gas
as illustrated in Figure 1, thus producing minimal emissions of nitrogen oxide and sulfur
oxide compared to incineration, the most common process in the industry. It is defined as
the sum of a series of parallel and subsequent reactions that take place in the pyrolysis
reactor [15]. The products obtained with this process can be easily handled, stored, and
.transported which increases the applicability of this method [16]

.Pyrolysis types and reactor configuration

There are many classifications of types of pyrolysis depending on the operating conditions,
such as the heating rate, temperature, and the gases residence time. In general, pyrolysis is
classified as either fast or slow. Regarding the environment used in the process, it can be
classified as oxidative pyrolysis, steam pyrolysis, hydro pyrolysis, catalytic pyrolysis and
vacuum pyrolysis, and also depending on the heater system as the microwave or plasma
pyrolysis. Conventionally, fluidized and entrained bed reactors are associated with fast
pyrolysis whilst fixed bed reactors (FBR) are associated with slow pyrolysis (a batch or semi-
.batch process)

Other types of reactors such as the rotating cone (usually used for liquid production since
the heating rate is high and the vapor residence time is relative short), may also be
.categorized as carrying out fast pyrolysis [17]
.Slow pyrolysis

This type of pyrolysis, as the name suggests, considers a slow thermal decomposition at low
temperatures. It is characterized by low heating rates, relatively long solid and vapor
residence times, and sometimes by low temperature. Longer residence times result in
leading secondary conversion of primary products, yielding more coke, tar, as well as
thermally- stable products. This fact is why slow pyrolysis is sometimes referred to as
carbonization. Unlike fast pyrolysis, the objective of slow pyrolysis is the char production,
.although tar and gases are also obtained but not necessarily recovered [17]

.Fast pyrolysis

In contrast to slow pyrolysis, fast pyrolysis indicates a rapid thermal decomposition

characterized by higher heating rates. This process usually requires a feedstock with small
particle sizes and specially-designed devices to allow quick removal of the vapors released.
Fast pyrolysis is recognized as an effective conversion route for the production of liquid
fuels, chemicals and derived products with higher yield (usually around 50–60 wt. % for
.rubber feedstock) [17]

.Rotary kiln pyrolysis

A rotary kiln is basically a rotating inclined cylinder as illustrated in Figure 2. Solid retention
time in a kiln is an important design factor and is set by proper selection of the diameter,
length, speed, and slope of the internal design. Most important, for the required chemical
reaction(s) to take place, solids must be heated to a specific point. There are two basic types
of rotary kilns; direct fired and indirect [18]. Rotary kiln reactors are the most common
.reactor used for pyrolysis in the industry

.Fixed bed pyrolysis

Fixed bed pyrolysis reactors are mostly used by researchers in laboratory experiments
because they are easy to construct and operate. The majorities of reactors are made of
stainless steel or quartz and glass [18]. The major drawback of fixed bed pyrolysis is the poor
heat transfer to large volume of tires. Thus, shredding of tires to small particles is needed.
Figure 3 shows the reactor configuration
.Fluidized bed pyrolysis

Studies regarding fluidized beds are limited due to the difficulty of their operation. Figure 4
shows the reactor configuration. However, fluidized bed reactors are advantageous due to
their: long residence time which contributes to secondary reactions and lower temperature
and heating rate that favor carbonization which reduces oil yield (perfect if the product
targeted is the gas). Pyrolysis in a fluidized bed is characterized as fast pyrolysis directly
producing a liquid fuel, which is beneficial when tire resources are remote from where the
energy is required, since the liquid can be readily stored and transported [18]

.Ablative reactor pyrolysis

Compared to other types, ablative pyrolysis is not common. It is defined as the

phenomenon occurring when a solid, exposed to high external heat flux density producing
solids, liquids and/or gases can be rapidly and continuously removed from the reactor.
Ablation can be exploited for carrying out the fast pyrolysis of materials such as tires. Tires
are pressed against a hot surface (contact ablative pyrolysis) or intercept a concentrated
.radiation (radiant ablative pyrolysis) [18]

.Flash pyrolysis

Flash pyrolysis is characterized by high heating rates, temperatures between 450°C to 600°C
and short residence times of less than one second which make these conditions perfect to
prevent cracking of the gases into noncondensable gases, maximizing the liquid product
.yield [18]. Figure 5 shows the flash pyrolysis reactor

.Catalytic pyrolysis

Catalytic pyrolysis is becoming an important area of recent investigation and is considered a

very promising field. The influence of the catalyst is to reduce the yield of oil with a
consequent increase in the gas yield. Thus, the catalyst causes an increase in the cracking of
hydrocarbons into shorter chain lengths, which decreases oil yield while increasing the
amount of gases evolved [23]. The most used catalysts are Y-type zeolite, ZSM-5, and Al2O3.
In addition, single ring aromatic hydrocarbons, benzene, toluene and xylenes present in the
oils, can noticeably increase in the presence of the catalyst. Naphthalene and alkylated
.naphthalene show a similar increase in concentration when a catalyst is present [18]

.Steam pyrolysis

Steam pyrolysis of tires for oil production was also investigated by some researchers. One of
the advantages of steam pyrolysis is the reduction of pyrolysis temperatures needed by up
to 150°C, compared with steam-free pyrolysis. This is due to the ability of steam to diffuse
into the tires and release pores and displace volatiles. Moreover, the steam reduces the
partial pressures of pyrolysis gases through dilution and improves the concentration
gradient flow from the tires. Therefore, the mass transfer of gases from the tires is improved
.during the process [23]

.Plasma pyrolysis

Thermal plasma pyrolysis defined as a solid reaction with limited oxygen and high
temperatures to produce gaseous and solid products. When tire particles are placed in
plasma, the volatile matter is released and cracked, raising the amount of hydrogen and light
hydrocarbons such as methane and acetylene. There are four main stages of plasma
pyrolysis : extremely fast particle heating originating from plasma jets, a massive release of
volatile matter from tire particles, very fast gasification of the homogenous phase, and
finally, rapid heating and mass exchange. There are many advantages of plasma pyrolysis
such as its high heating transfer rate, the desired properties of pyrolysis products, and the
high possibility of eliminating dangerous substances. However, a plasma pyrolysis reactor
requires a high amount of energy to achieve the required conditions. There are two major
.products from plasma pyrolysis: gas and solid (char) [18]

.Molten salt pyrolysis

Molten-salt destruction is an alternative pyrolysis method. In this process, a molten and

turbulent bed of salt is used, such as sodium carbonate, to destroy hazardous materials.
Shredded solid waste is injected with air under the surface of the molten salt. Hot gases
(carbon dioxide, steam, and unreacted air) rise through the molten salt bath, and pass
through a secondary reaction zone and through an off-gas cleanup system before
discharging to the atmosphere. The remaining pyrolysis by-products; react with the alkaline
molten salt forming inorganic products that are retained in the melt. Spent molten salt
.containing ash; is drawn away from the reactor, cooled, and placed in landfills [18]

.Microwave pyrolysis

Microwave pyrolysis involves uniform and rapid thermal energy being applied to the waste
tires. This process has a high heating efficiency and short reaction time. Thus, polymers like
waste tires can be easily 21 heated regardless of their low thermal conductivity. However,
any type of rubber used in the microwave process must be sufficiently polar in structure so
that the microwave energy can be absorbed at the appropriate rate to make de-
.vulcanization viable [18]

.Co-pyrolysis

Vehicle and truck tires with waste lubricant oil (WLO) are co-pyrolyzed in a fixed bed reactor
at temperatures from 550 to 800°C. Co-pyrolysis with WLO produces more oil than pyrolysis
of tires alone. However, copyrolysis of car tires with WLO produces less liquid than co-
pyrolysis of truck tires with WLO. Although the addition of WLO does not enhance the
degradation of tires during pyrolysis, co-pyrolysis oils consist of higher amount of lighter
fraction than commercial diesel. That means; the addition of scrap tires into WLO increases
.the degradation of heavy fractions in WLO [23]

M. Islam, M. Islam, N. Mustafi, M. Rahim and H. Haniu, "Thermal Recycling of Solid Tire ]15[
Wastes for Alternative Liquid Fuel: the First Commercial Step in Bangladesh," Procedia
.Engineering, vol. 56, pp. 573-582, 2013

H. Aydin and C. Iilkilic, "Optimization of Fuel Production from Waste Vehicle Tires by ]16[
Pyrolysis and Resembling to Diesel Fuel by Various Desulfurization Methods," Fuel, vol. 102,
.p. 605–612, 2012

J. D. Martinez, N. Puy, R. Murillo, T. Garcia, M. V. Navarro and A. M. Mastral, "Waste ]17[

Tyre Pyrolysis–A Review," Renewable and Sustainable Energy Reviews, vol. 23, pp. 179-213,
.2013

N. Antoniou and A. Zabaniotou, "Features of an Efficient and Environmentally ]18[

Attractive Used Tyres Pyrolysis With Energy and Material Recovery," Renewable and
.Sustainable Energy Reviews, vol. 20, pp. 539-558, 2013
A. Quek and R. Balasubramanian, "Liquefaction of Waste Tires by Pyrolysis for Oil and ]23[
.Chemicals—A Review," Journal of Analytical and Applied Pyrolysis, vol. 101, p. 1–16, 2013