Progress in Energy and Combustion Science 85 (2021) 100915

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Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

Combustion engine applications of waste tyre pyrolytic oil

Maciej Mikulski a,b, Marta Ambrosewicz-Walacik c, Jacek Hunicz d,∗, Szymon Nitkiewicz e,f
a
School of Technology and Innovation, Energy Technology, University of Vaasa, Wolffintie 34, FI-65200 Vaasa, Finland
b
Vaasa Energy Business and Innovation Centre (VEBIC), Yliopistonranta 3, FI-65200 Vaasa, Finland
c
Independent researcher
d
Faculty of Mechanical Engineering, Lublin University of Technology, Nadbystrzycka 36, 20-618 Lublin, Poland
e
Faculty of Technical Sciences, University of Warima and Mazury, Oczapowskiego 11, 10-719 Olsztyn, Poland
f
Collegium Medicum, University of Warima and Mazury, Warszawska 30, 10-082 Olsztyn, Poland

a r t i c l e i n f o a b s t r a c t

Article history: There is abundant worldwide research into combustion engine applications for tyre pyrolysis oil (TPO).
Received 13 March 2020 However, many of these studies demonstrate conflicting or ambiguous results, so although the huge num-
Accepted 20 February 2021
ber of used tyres promises good availability for TPO, its role as fuel for transport applications is still
uncertain. This reviewś goal is to clarify the case for TPO as transport fuel by means of a critical, wide-
Key words: ranging and updated review of TPO’s engine applications. The work gathers, collates and analyses the re-
Tyres sults of over 200 influential original research papers, aiming to answer the governing research questions
Pyrolysis related to TPO production and quality, post-processing and quality improvement and its final end-use
Pyrolytic oil engine validation. The work re-evaluates the environmental aspects of TPO technology, setting it against
Life cycle analysis
the latest backdrop of growing climate change concern and the urgency to find alternative fuels. The hard
Fuel quality
economics of TPO are also addressed, for example, assessing other end-of-life tyre management routes
Fuel characterisation
Combustion engines and competing fuel alternatives.
Compression ignition The critical discussion on the key issues, including the most relevant drivers and boundaries, points
Emissions towards TPO’s use as a fuel component in marine, off-road and heavy-duty road applications. The re-
sults indicate that state-of-the-art production methods yield fuel that could be used directly in bunkering
chains for marine transport as low-sulphur fuel oil. Discussion reveals that automotive applications are
limited to blends not exceeding 10% tyre pyrolytic oil: sulphur and polyaromatic hydrocarbons contents
and particulate emissions are the main constraints. Pyrolysis process efficiency is high and feedstock for
TPO is both available and flexible. Waste tyre-derived pyrolytic oils could function as a supplementary
solution to biofuels, blended to take advantage of their complementary properties.
The particular added value of this review is that it bridges the latest knowledge from several domains
related to TPO fuel: industrial management, process chemistry, fuel science and combustion/engine re-
search. The resultant analysis is expressed in terms that are accessible to all those domains. It underlines
how studies from an individual domain perspective fail to produce the holistic view. The review creates
a route towards modern multidisciplinary research supporting TPOś role in global transition to circular
economy.
© 2021 Elsevier Ltd. All rights reserved.

Contents

1. Introduction and background. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

1.1. Waste tyres - the scale of the problem, recycling routes and legislation framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2. Waste tyre pyrolytic oil as a fuel for combustion engines: drivers and boundaries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3. Motivation, knowledge gaps and detailed scope of the present work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2. The state of the art in tyre pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1. From waste tyres to fuel: process outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2. Mechanisms of tyre pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

∗
Corresponding author.
E-mail address: j.hunicz@pollub.pl (J. Hunicz).

https://doi.org/10.1016/j.pecs.2021.100915
0360-1285/© 2021 Elsevier Ltd. All rights reserved.
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al. Progress in Energy and Combustion Science 85 (2021) 100915

2.3.Tyre pyrolysis technology and the effect of operational parameters on product composition . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3.1. Temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3.2. Feedstock size and heating rate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3.3. Inert gases and catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3.4. Feedstock type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3.5. Co-pyrolysis of tyres with other materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.4. TPO production efficiency and life cycle analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.4.1. TPO energy and exergy efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.4.2. Tyre pyrolytic plant life cycle analysis and total cost of ownership . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.4.3. TPO vs other fuels - remarks on the economics and GHG footprint . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.5. General characterisation of pyrolysates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5.1. Solid fraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5.2. Gaseous fraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5.3. Liquid fraction (tyre pyrolysis oil – TPO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3. Pyrolytic oil as engine fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.1. Properties of crude TPO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2. Properties of TPO distillates (DTPO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.3. Quality improvement measures for TPO/DTPO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.4. Blending with other fuels and TPO addification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4. Engine tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.1. Mixture formation and combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.2. Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.2.1. Nitrogen oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.2.2. Particulate matter and smoke opacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.2.3. CO and unburnt hydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5. A critical overview and outlook on further research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Appendix. Type of reactors used during pyrolysis and most relevant process conditions affecting TPO yield . . . . . . . . . . . . . . . . . . . . 35
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

1. Introduction and background
Global demand for crude oil continues to increase, propelled by
economic and population growth. Meeting the Paris Agreement’s
CO2 (carbon dioxide) reduction goals requires radical changes
around the world. A significant reduction in fossil fuels is needed
across all fronts, from power generation to manufacturing and
transport. Although renewables’ share is increasing at a rate of 4%
per year, it is foreseen that in 2030 they can still only cover half of
the global increase in energy demand [1].
Looking at fuel production, growth of gasoline consumption is
being retarded mainly by fast progress of electrification in the
light-duty transport sector. Heavy-duty transport continues to rely
on diesel fuel (DF) due to its high energy density and the high
efficiency of compression-ignition (CI) engines [2]. Here, the fast
track towards sustainability is mainly via scaling up new gen-
eration drop-in fuels that can be readily used in existing fleets.
Currently, there are two feasible renewable fuel production tech-
nologies that have reached industrial-scale production volumes:
transesterification and hydrotreatment of carboxylic acids. Trans-
esterification, producing mainly fatty acid methyl esters (FAME),
is more widespread due to the simplicity of the process. Hy-
drotreatment, yielding hydrotreated vegetable oil (HVO) is less
common but offers greater potential because the end product
has higher quality than esters or even diesel [3]. Moreover, HVO
can be produced using existing refinery infrastructure, provid-
ing high process efficiency. Both processes have one significant
downside: limited flexibility on feedstock, which heavily relies on
first-generation bio-components, potentially competing with food
production [4].
Pyrolysis is another promising concept for renewable diesel and
other types of fuels. The main advantage here is that a variety of
bio and synthetic waste materials (plastics, rubber, etc…) can be
used in the same reactor. More importantly, recent works indicate
a synergistic effect when co-pyrolysis of bio and synthetic material
is applied, reporting potential for process efficiency enhancement
and increasing the fuel mass yield [5].
Another aspect of the sustainability challenge is efficient re-
cycling of waste materials. Management of automotive shredder
residue and management of end-of-life tyres (ELTs) are of partic-
ular concern [6,7]. Waste tyres cannot be used in landfill due to
poor biodegradability and environmental hazards like fire and wa-
ter stagnation (supporting the proliferation of insects and bacte-
ria) [8]. The complex material structure which makes ELTs difficult
to process also creates a variety of residual streams. Steel fibres,
shreds, oils and carbon filler can be recovered from used tyres.
Tyres’ high calorific value make them suitable as fuel substitute
in waste-to-energy plants or as a feedstock to alternative thermo-
chemical conversion plants for both energy and carbon material
production [9].
In the above context, pyrolysis of ELTs is currently a widely ex-
plored topic, with many works focusing on improving the process
efficiency and tyre pyrolysis oil (TPO) fraction yield [10–12]. At the
same time, crude TPOs and also their different distilled fractions
have been studied by many researchers as standalone fuel [13,14].
Others have studied the large-scale blending of TPO with other fos-
sil fuels [15,16] and biofuels [17], or, in case of light distillates, as
a renewable fuel additive (improver) [18]. This research involves
both laboratory analysis of fuel properties and evaluation of per-
formance by engine tests. Evaluating the current status of engine
research is particularly difficult due to a diversity of engine plat-
forms used in tests. For instance, contradictory results are quite of-
ten reported when exhaust emission effects are considered [13,15].
Similar discrepancies can be observed in terms of crude TPO pro-
duction, fractionation and quality improvement. These ambiguities
result from differences in feedstocks used, processing technology,
engine displacements and their technology level or the combustion
modes used during testing.

2
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al. Progress in Energy and Combustion Science 85 (2021) 100915

Nomenclature and abbreviations SiO2 silica

SOC start of combustion
Al2 O3 aluminium oxide SOI start of injection
BF blast furnace SO3 sulphur trioxide
BMEP brake mean effective pressure SOX oxides of sulphur
BR butadiene rubber TGA thermogravimetric analysis
bTDC before top dead centre TiO2 titanium dioxide
C carbon TME tallow methyl ester
CA crank angle TPO tyre pyrolysis oil
CaCO3 calcium carbonate UCOME used cooking oil methyl ester
CaO calcium oxide UHC unburnt hydrocarbons
Ca (OH)2 calcium hydroxide ZnO zinc oxide
CCAI calculated carbon aromaticity index ZSM-5 zeolite Socony Mobil-5
CH3 COOH acetic acid
CI compression ignition
CN cetane number The objective of this work is a comprehensive assessment of
CO carbon monoxide the current state of the art in ELT conversion to mechanical power
CO2 carbon dioxide through internal combustion engine applications. The introduction
CR common rail section provides a background for the present work. It describes
DF diesel fuel the overall scale of the problem and its legislation boundaries,
DTPO distilled tyre pyrolytic oil placing pyrolysis in the context of other re-processing technolo-
DMC dimethyl carbonate gies. The introduction is summarised by discussing the premise of
DTG derivative thermogravimetry the present research in terms of its significance and the particu-
EGR exhaust gas recirculation lar knowledge gaps it aims to fill. The main body of the work re-
ECA Emission Control Area views the current state of the art in tyre pyrolytic fuels, following
EEDI energy efficiency design index the process chain from production (Section 2), through analytics
ELT end-of-life tyre and upgrading (Section 3) and finishing with end-use engine per-
EPR extended produced responsibility formance (Section 4). The work is summarised with an overview
ETRMA European Tyre and Rubber Manufacturers Asso- and outlook section (Section 5), culminating with conclusions.
ciation
EU European Union 1.1. Waste tyres - the scale of the problem, recycling routes and
FAME fatty acid methyl esters legislation framework
Fe2 O3 iron oxide
H hydrogen The number of used tyres in the European Union (EU) is trend-
H2 molecular hydrogen ing upwards, mainly because of the developing road transport and
H2 O2 hydrogen peroxide light-duty automotive sectors in eastern Europe. A report from
H2 S hydrogen sulphide the European Tyre and Rubber Manufacturers’ Association (ETRMA)
H2 SO4 sulphuric acid indicated there were 2.88×109 kg of used tyres (EU, Norway,
HFO heavy fuel oil Switzerland and Turkey) in 2013 and 3.58×109 kg in 2018, which
HHV higher heating value gives an average growth rate of 4% per year [19,20] A similar trend
HRR heat release rate is observed on a worldwide basis, with a global amount of ELT
HVO hydrotreated vegetable oil generated estimated in 2019 to be 29.1×109 kg [21].
IMEP indicated mean effective pressure Currently, the management of used tyres in most countries is
IMO International Maritime Organisation regulated by legislation. A comprehensive review of specific EU
JME jatropha methyl esters regulations affecting tyre deposition and treatment can be found in
K2 O potassium oxide [9]. Of over 15 sets of ELT legislation, certainly the most important
LHV lower heating value one is the Directive on the Landfill of Waste 10 0 0/31/EC, issued in
MgO magnesium oxide 1999. This initiative basically prohibited stockpiling of whole tyres
MJ/kg megajoules per kilogram in landfills, starting from July 2003, and scrapped tyres from July
MJ/Nm3 megajoules per normal cubic metre 2006. As a result, in 2010, 96% of the EU’s used tyres were re-
N nitrogen covered for residual management [19]. The EU Circular Economy
NaOH sodium hydroxide Package of December 2015 also helped close the loop in used-tyres
NCV net calorific value management. It put particular emphasis on product reuse and sup-
NEDC new European drive cycle porting sustainability by extending the product’s lifetime. Reuse,
NiMo-Al2 O3 nickel-molybdenum on alumina export and retreading (all classified as reuse) cumulatively account
NO nitric oxide for around 20% of all recycled tyres. In the case of ELTs (tyres that
NOX oxides of nitrogen cannot be reused), ERTMA identifies material recycling and energy
NBR natural polybutadiene rubbers recovery as primary handling routes. Fig. 1 depicts how utilisation
P2 O5 phosphorus pentoxide of waste tyres evolved as a consequence of legislation over the
PAH polycyclic aromatic hydrocarbons years. It is based on merged data from sources referenced in the
PM particulate matter figureś caption.
PRR pressure rise rate Generally, the ELT market is currently stable in Europe with
rpm revolutions per minute country-to-country variation being more significant than the
SBR styrene-butadiene rubber change in the global trend. Material recycling is now the main han-
dling route (50%), followed by energy recovery (29%). The ELT man-

3
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 1. ELT management routes and their percentage contribution in handling available material in EU. Based on data merged data from [22] - until 2009; [23] – until 2015;
[24] – year 2016, [25] – year 2017, [20] – year 2018.
agement system in EU countries consists of three different models:
Extended Producer Responsibility (EPR), the liberal system (free
market) and the tax system. Under the first system, introduced
in the majority of EU member countries, manufacturers and im-
porters of tyres are obliged to ensure that tyre wastes are dis-
posed of in an appropriate manner that does not harm the envi-
ronment [19]. The free-market system assumes that ELTs are im-
portant sources of valuable raw materials and that their recovery
and recycling are profitable, so the onus rests on commercial com-
panies to capture and harness the ELTs. That system operates in
Austria, Switzerland and Germany. In the case of the tax system,
applied in Denmark and Croatia, recovery/recycling organisations
are responsible for used-tyres management. This is financed by the
state via a tax levied on tyre manufacturers [19].
Depending on the country/system, different stakeholders take
primary responsibility for management of ELTs and, ultimately, for
phasing-in new processing technologies. One of the main barriers
to application of tyres pyrolysis is unclear legal process definition.
According to the EU, depolymerisation of tyres by gasification or
pyrolysis is classified as a destructive process, equivalent to in-
cineration (thermal waste treatment with or without heat recov-
ery). In fact, pyrolysis of ELTs should be considered as an energy
and material co-recovery process. Pyrolysis oil (TPO) and remaining
gas both can be used as energy sources or inputs for new materi-
als synthesis [26]. Thus, pyrolysis shows considerable environmen-
tal benefits over combustion/incineration which releases significant
amounts of CO2 and extremely toxic substances. The former con-
tributes to climate change; the latter are dangerous for the envi-
ronment and human health [27,28]. Still, the emission legislation is
quite liberal for waste incineration processes, effectively inhibiting
the more energy-efficient and environmentally friendly processes.
In summary, current EU legislation suppresses the opportu-
nity for tyre pyrolysis to take a major share in ELTs management.
To address this, closer collaboration between the joint alternative
management system of each country and the research community
should be promoted. A transition from Extended Producer Respon-
sibility to the free-market system could offer a better opportunity
for TPO. The ERTMA [29] and some research groups [8] are lobby-
ing for this, aiming to create a value-based drive towards more ef-
ficient and socially acceptable solutions in waste tyre management.
1.2. Waste tyre pyrolytic oil as a fuel for combustion engines: drivers
and boundaries
For simplicity, this discussion concerning the drivers and
boundaries for TPO as engine fuel focuses purely on CI (diesel) en-
gines. These have the biggest demand for alternative fuels, as in-
dicated in Section 1. Fossil DF, and on the alternative side, FAME
and HVO, currently the most feasible alternative for CI engines, are
mentioned in these discussions as references.
4
Progress in Energy and Combustion Science 85 (2021) 100915
In terms of drivers, TPO fuels face the same economics as other
alternative fuels. Global fuel demand is rising by around 10% per
year and at the same time crude oil exploration is becoming more
expensive, increasing the economic feasibility for alternatives
[1]. This momentum is reinforced by numerous CO2 reduction
initiatives, with the 2015 Paris agreement being the most relevant
globally.
Tyre pyrolytic oils are produced from waste material and so are
classified as second-generation fuels. As such, they have a more
favourable CO2 factor on a well-to-wheel basis than popular biofu-
els FAME and HVO, assuming these are still majorly produced from
first-generation components (competing with food production) like
palm or rapeseed oil [30]. However, it is necessary to stress that a
detailed GHG emissions life cycle analysis for both fuel categories,
TPO and bio-oils, is extremely complex and heavily dependent on
geo-economic factors (see Section 2.4 for details).
The biggest challenge for FAME and HVO is limited flexibility
of feedstock. Data in the previous section and the percentage of
collected ELTs [20,31] suggest that waste tyres potentially available
for TPO production in 2019 could be estimated at around 2.7×109
kg per year in Europe alone, and growing at 4% per annum. This
is assuming the current ELTs stream split for applications other
than energy. For comparison, European availability of oilseeds and
vegetable oils (which currently underpin over 86% of biofuel pro-
duction) accounts for 50×109 kg, but only around 13% of that (i.e.
about 6.5×109 kg) is available for fuel purposes due to strong com-
petition with food production [32]. Waste tyre availability for en-
ergy generation would increase if more sustainable and econom-
ically feasible solutions are developed, making this use of ELTs
more attractive than direct material recovery. Pyrolysis (and gasifi-
cation) also provide feedstock flexibility, meaning the same reactor,
in principle, can be used to convert biomass, plastics and rubbers
from waste tyres. This co-pyrolysis of different feedstocks provides
further pathways to improve TPO composition and yield [33].
Aside from the general push to cut CO2 emissions, the light-
and heavy-duty road transport sectors have their own country-
specific (or EU-wide) fleet-level CO2 targets. The off-road sector is
currently discussing the adoption of similar limits, while the ma-
rine sector has its EEDI (Energy Efficiency Design Index). Without
going into detail, it is sufficient to say that, because all initiatives
refer to tank-to-wheel CO2 emissions, none of them supports the
development of diesel-like alternative fuel. This applies equally to
TPO, FAME and HVO since all have a similar carbon to hydrogen ra-
tio, dependent more on the feedstock and refining processes rather
than on the fuel category itself.
The constraints for TPO as a fuel are mostly dependent on the
domain where the fuel is intended for use. Table 1 outlines the
selected physicochemical properties of the fuels determined by the
most relevant standards in different application domains. Note that
the automotive and marine fuel regulations are considered the
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al. Progress in Energy and Combustion Science 85 (2021) 100915

Table 1
Selected requirements for CI engine fuels in different transport domains with respective standards [34–38].

Sector Norm/standard Density Kinematic viscosity Sulphur content CN/CCAI Flash point Water content
Units / conditions / limits [kg/m3 ] @150 C [mm3 /s] @400 C [ppm] [-] min. [°C] min. [specified] max. Comments

On- CEN EN590 820-845 2-4.5 10 51 55 200 [mg/kg] EU commercial

road Diesel
CEN EN 14214 860-900 3.5-5 10 51 120 500 [mg/kg] EU neat biodiesel
ASTM D975 No. 2-D n/a 1.9-4.1 15 40 52 0.05 US commercial
[%vol.] Diesel
ASTM D6751 09 n/a 1.9-6 15 47 93 0.05 US neat biodiesel
[%vol.]
Off- DIN 51605 n/a 910-925 36 10 39 101 750 [mg/kg] german standard
road/ for SVO fuel
other applications
ASTM D975 No. 4-D n/a 5.5-24 n/a 30 55 0.05 heavy distillate for
[%vol.] const. speed eng.
Marine ISO 8127 ISO-F-DFA 890 max. 2-6 1000 40 60 n/a distillate fuels;
ISO 8127 ISO-F-DFB 900 max. 2-11 1500 35 60 n/a selected categories
∗
ISO 8127 ISO-F-RM(A-E) 920 -991 10 -180 @50°C statutory 850-860 (CCAI) 60 0.05 residual fuels;
[%vol.] selected categories
∗
ISO 8127 ISO-F-RMG 991 max. 180-700 @50°C statutory 870 (CCAI) 60 0.05
[%vol.]
∗
For marine residual fuels, the customer defines the sulphur content in accordance with relevant statutory limitations.

two boundary regimes for fuel applicability (least and most in-
clusive, respectively) and from this perspective, we discuss them
more thoroughly. Selected regulations for the off-road sector are
provided for reference.
The EN 590 standard defines the fuel properties for compres-
sion ignition engines for European road transport. In the US, the
ASTM standard for automotive diesel fuels (No. 2-D) puts similar
requirements on fuel quality, although there is one major differ-
ence: ASTMś minimum cetane number (CN) is significantly lower
than that of EN590. Generally, a well-known fact is that crude TPO
complies with neither EN 590 nor ASTM D-2 as a standalone, drop-
in fuel because of its high viscosity and large amounts of impuri-
ties [17]. Thus, most authors typically consider blending TPO with
DF and/or other alternatives. In terms of alternatives, note that
neat FAME as an infrastructurally mature fuel category has sep-
arate quality standards both in the EU and the US. For automo-
tive fuels, these standards are quite strict and yet EN590 still limits
the blending of FAME in commercial diesel to 7% by volume, while
ASTM D975 imposes a 5% limit.
The other commonly considered option is further refining to
produce TPO more compliant with EN 590, with distillation as one
of the more straightforward methods [39]. Poor miscibility with
diesel is another constraint if TPO is considered as an additive
[40]. In terms of further upgrading TPO, standard refinery infras-
tructure can be used to treat crude TPO with similar processes as
those for fossil crude oil or vegetable oils, including hydrotreat-
ing, to arrive at ultra-clean distillates. These are covered in detail
in Sections 3 and 4, considering both energy demand/quality and
end-use in engines.
The marine domain is still quite inclusive in terms of fuel qual-
ity. ISO 8217 is the current standard governing bunker fuel qual-
ity, and crude TPO, depending on the process and feedstock qual-
ity, can be directly considered in one of the distillate or residual
marine fuel categories (consult Table 1). Also, heavy fractions from
distilled tyre pyrolysis oil (DTPO) can be used to valorise the off-
stream from lighter distillates production. High viscosity and high
contamination do not pose a challenge, because marine diesel en-
gines have on-board fuel pretreatment using centrifugal separa-
tors and preheaters. However, marineś sulphur legislation might
be challenging for TPO. The 2020 International Maritime Organi-
zation (IMO) sulphur cap limits a fuel’s total sulphur content to
0.5% on all international waters [41,42]. In the IMO’s Emission Con-
trol Areas (ECAs) the fuel’s sulphur limit is only 0.1% (10 0 0 ppm)
[41]. Desulphurisation methods for TPO are reviewed in detail in
Section 3.3.
Aside from the fuel standards outlined above, emissions legisla-
tion has an indirect impact on fuel phase-in. Currently, all domains
where combustion engines operate are subject to strict emission
limits. In Europe, Euro VI is in force for light- and heavy-duty ve-
hicles, limiting emissions of nitrogen oxides (NOX ), unburnt hydro-
carbons (UHC), carbon monoxide (CO) and particulate matter (PM).
Stage V regulations cover the off-road sector (including inland wa-
terways), but impose slightly less stringent NOX , UHC and CO lim-
its, dependent on engine power output. In the marine sector, the
IMO imposes NOX limits: Tier III regulations apply in ECAs and
Tier II regulations apply in waters outside the ECAs. For a com-
plete overview of current emission norms, the reader is referred to
DieselNet: Engine & Emission Technology Online [43].
The case of how emission legislation either supports or sup-
presses individual fuel alternatives has three dimensions. One is
the engine-out emissions (i), where different fuels have a different
internal predisposition to creating certain hazardous species. The
second factor (ii) relates to how the fuel affects engine perfor-
mance, since all emission limits are given in values specific to
generated power. Finally, (iii) all of the discussed emission legis-
lation currently in force, except IMO Tier II, require some sort of
exhaust gas aftertreatment for CI engines to meet the imposed
limits. However, TPO can have a profound effect on performance
of catalysts used in aftertreatment. Notably, sulphur is limited in
automotive diesel fuel because it is a catalyst poison for diesel
oxidation catalysts, catalysts for NOX reduction by urea SCR, and
NOX adsorbed catalysts. The EU 10 ppm and the US 15 ppm sul-
phur limits are thus not negotiable and would have to be met for
use in these applications. Section 4 of this review (Engine tests)
looks in more detail at the TPO studies that evaluated legislated
and unlegislated emissions.
1.3. Motivation, knowledge gaps and detailed scope of the present
work
The above introduction clearly shows that ELTs are an attrac-
tive feedstock for energy generation. Pyrolysis as fuel production
technology has potential to combine clean utilisation of tyres with
an efficient way of material recycling and energy recovery, while
avoiding the food-fuel dilemma. Furthermore, the flexibility of the
reactor permits greater feedstock availability through co-pyrolysis
of other synthetic waste (plastics) and biomass. In the face of the
global CO2 reduction targets, this seems to be increasingly recog-
nised. The main hurdles for TPO to overcome relate to legislation,
production technology development and the technical aspects of

5
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 2. Tyre decomposition through the pyrolysis route.
its use as an engine fuel. In all of those fields, there is currently
rapid development regarding TPO and many research works are
bringing new insights, greater knowledge and more efficient solu-
tions. This is communicated in original research papers but there
are also broader review works that summarise progress. Reviews
by Torretta et al. [8] and Antoniou and Zabaniotou [9] provide good
insight into legislation, feedstock availability and detail forecasts
for ELTs management stream. The latter review by Antoniou and
Zabaniotou [9] is by far the most comprehensive study covering
the topics of tyre waste handling through pyrolysis. It has an ex-
tensive review of the production process, pyrolysis kinetics and its
products, including TPO. This study gives an excellent overview of
the topic yet it does not cover the fuel applications in great depth
and does not reflect the current state of the art in end-user val-
idation of TPO fuels through engine tests. Furthermore, it is now
seven years since the study was published, a period that has seen
significant development in tyre pyrolysis technology.
In terms of the fuelling applications, the knowledge gap is par-
tially filled by a more recent review by Czajczyńska et al. [44].
This work is very detailed but focuses solely on the gaseous frac-
tion. Furthermore, the combustion applications are limited solely
to furnace combustion, providing heat to the pyrolysis process it-
self. Due to higher energy density (by volume) and easier logistics,
it is the liquid fraction of pyrolysis (TPO), not the gaseous fraction,
that holds potential as a transport fuel.
The last decade has seen a surge in research into TPO’s use
as combustion engine fuel [45]. Evaluating the current status is
very difficult due to the wide discrepancy in TPO quality, differ-
ent blending strategies and the variety of engine platforms used
hitherto. It was this combination of rapid progress, coupled with
the difficulty of building a complete and accurate picture from so
many disparate studies of TPO’s use for combustion engine appli-
cations, that motivated us to bridge this substantial knowledge gap.
The research questions addressed here are as follows:
i What is the current view on TPO well-to-tank environmental
impact and economic feasibility?
ii What is the progress in pyrolysis technology with respect to
maximising the TPO yield and resulting fuel quality?
iii What are the available TPO-upgrading technologies and what is
their effect on the end fuel quality?
iv What is TPOs potential as a fuel component?
v How do different fuel compositions of TPO and TPO-derived fu-
els perform in the engine in terms of combustion characteris-
tics, efficiency and emissions?
6
Progress in Energy and Combustion Science 85 (2021) 100915
As well as finding knowledge gaps, we recognize that there is
not widespread familiarity with TPO as an alternative fuel for com-
bustion engines. So, aiming to build a complete picture, this re-
view also provides an updated description of the state-of-the-art
process for tyre pyrolysis. The level of detail is sufficient to under-
stand the dependencies and to valorise the off-streams. This is cov-
ered in Section 2, along with providing the input necessary for the
research question (i) and (ii). Consequently, the input for research
questions (iii) and (iv) is gathered in Section 3. Section 4 provides
a critical review of all aspects of the research question (v). The
introduction section provides the necessary legislative framework
to conduct the review in all sections. Finally, the discussion and
summary in Section 5 combine the individual inputs into a concise
roadmap of TPO fuelling applications.
The work is directed to scientists and engineers working in the
fuel industry and engine technology. Automotive and aviation sec-
tors are already claiming over 90% of available biofuel supplies,
leaving limited alternatives on the liquid fuel side for the marine
and off-road sectors. Thus, these sectors might be particularly in-
terested in the work. Hence the discussion is led with both auto-
motive and bunkering fuel legislation in mind. All sectors are con-
sidered when assessing engine emissions.
2. The state of the art in tyre pyrolysis
2.1. From waste tyres to fuel: process outline
Tyre pyrolysis can be described as a process of thermal decom-
position of solid organic compounds of ELT within limited access to
oxygen. During the thermo-chemical reactions, a series of volatile,
liquid and solid components are being produced [46]. Fig. 2 shows
a typical tyre material decomposition route through pyrolysis.
Most often the tyres’ steel components are removed before
thermal processing and rubber parts are chopped, cleaned and
dried. Tyre pyrolysis generally consists of two stages: primary py-
rolysis and secondary cracking. During the initial phase, the vapour
or volatile products are generated, consisting of a variety of hydro-
carbons. From the point of view of this study, the liquid fraction -
TPO - is of main interest due to its possible application as a fuel.
The gaseous fraction can be reused to power the pyrolytic reactor
and make the process self-sustainable in energy terms. The solid
fraction (char) contains mainly carbon black, inorganic compounds
and many other carbon-based solids. Char can be utilised in a va-
riety of ways including substituting carbon black in the production
of new tyres. Therefore, by-products of the fuel recovery can pro-
vide energy savings as well as financial savings, when the entire
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 3. Typical TGA curve for pyrolysis process, based on [50].
process is evaluated. Notably, all material and energy recovery re-
duces carbon footprint.
Further processing can improve the properties of crude TPO.
That usually involves sulphur removal, distillation and cracking. In
practice, the end fuels for engines are produced from TPO via frac-
tionation (fraction blending to obtain desired fuel properties) and
thus are referred to as distilled tyre pyrolytic oil or DTPO [47].
2.2. Mechanisms of tyre pyrolysis
The process of thermal decomposition is most often charac-
terised by curves of the mass loss versus temperature. Thermo-
gravimetry, often called thermogravimetric analysis (TGA), is an an-
alytical technique that measures the mass over a period of time as
the temperature changes [48]. So-called derivative thermogravime-
try (DTG) functions, using the same method but with different pre-
sentation data, are used to show the rate of decomposition.
The tyre rubber pyrolysis process TGA curve in Fig. 3 exhibits
two main stages. The first is the slow stage, related to the decom-
position of oils, plasticisers and additives present in rubber. The
second is the active pyrolysis stage which involves cracking and
rapid decomposition of the other rubber components. The inter-
molecular associations and weaker chemical bonds are destroyed
during this second stage, resulting in gas and liquid fraction sepa-
ration. Beyond a certain temperature, active pyrolysis is essentially
completed, with only minor weight loss thereafter. This interpre-
tation of pyrolysis mechanisms was introduced by Williams and
Besler [48] and commonly adopted by others, e.g. Juma et al. [49].
Leung and Wang [46] stated that the first stage’s temperature
range was between 150°C and 350°C. This is where oil, moisture,
plasticisers and other additives decomposed. During the second
stage, above these temperatures but below 550°C, natural polybu-
tadiene and polybutadiene-styrene rubbers (NBR and SBR respec-
tively) were decomposed. Using DTG function, the maximum de-
composition rates were observed between 380°C and 450°C. Prad-
han and Singh [50] conducted a TGA analysis of waste bicycle tyres
in a laboratory-scale batch reactor. They observed that the first
stage of decomposition occurred at between 250°C and 380°C, fol-
lowed by the second stage at between 380°C and 550°C. This is de-
picted in Fig. 3. Above 550°C, the decomposition process was prac-
tically finished. TGA analysis conducted by Berrueco et al. [51] pre-
sented the thermal decomposition of a used car tyre (Michelin ra-
dial X type) sliced into 20 mm × 20 mm pieces. Decomposition
started at 200°C and complete conversion of the sample had oc-
curred when the temperature reached 500°C. However, the cited
authors isolated three stages. The first was between 200°C and
325°C, the second between 325°C and 400°C and the third stage
was between 400°C and 500°C. A DTG analysis of tyre pyrolysis by
7
Progress in Energy and Combustion Science 85 (2021) 100915
Seidelt et al. [52] proved that curves of a rubber DTG were char-
acterised by three temperature peaks, such as at 378°C, 458°C and
468°C. The first step was attributed to depolymerisation of the BR,
while at 468°C the decomposition of the cyclised and cross-linked
polymer residue was observed. Han et al. [53] however, conducting
a thermogravimetric mass spectrum analysis of waste tyres, iden-
tified four stages of this product’s thermal decomposition. The first
stage started below 320°C and contributed a minor reduction of
mass due to vaporisation of water and decomposition of plasticiser.
The next stage occurred at 320-400°C and related to the decompo-
sition of natural rubber. The third stage, at 400-520°C, involved the
decomposition of synthetic rubber. Very little weight loss was ob-
served during the fourth and final stage, above 520°C. The authors
associated the first three phases with the decomposition of differ-
ent polymer categories in the tyres: plasticisers (temperatures up
to 320°C), natural rubber (320-400°C), and synthetic rubber (400-
520°C). As a final note, it should be pointed out that in terms of
temperature range and ELT material degradation stages, there is a
good agreement within various studies.
For a more fundamental perspective, the TGA analysis is com-
bined with chemical kinetics studies. Four general mechanisms are
usually related to the decomposition of organic polymers: ran-
dom chain scission, end chain scission, chain stripping and cross-
linking [54]. Small molecules of volatile alkenes and cycloalkenes
are produced form the degradation of rubbers due to chain scis-
sion processes. The main products of chain alkenes are: 2-pentene,
1,3-butadiene and isoprene. These are formed from the depoly-
merisation of natural and synthetic rubber [55]. The main cyclic
alkenes, formed from the degradation of natural and synthetic
rubber or the cyclisation of chain alkenes consist of: 5-methyl-
1,3-cyclopentadiene, 1-methyl-1,4-cyclohexadiene, D-limonene and
cyclonona-1,2,6-triene [56,57]. As the reactor bed temperature in-
creases, alkenes and cycloalkenes undergo a series of reactions
such as the Dies-Alder reaction and aromatisation, forming ben-
zene and its derivatives. Along with the increase of the tempera-
ture, the ring-opening and recyclisation reactions yield the forma-
tion of other compounds belonging to alkenes and cycloalkenes.
Mentioned reactions mostly occur in the initial stage of the whole
process. During the second stage, benzene and its derivatives un-
dergo further reactions to form more aromatic compounds such as
polycyclic aromatic hydrocarbons (PAHs) [56], which are problem-
atic from the point of view of exhaust emissions. The favourable
conditions for aliphatic compounds aromatisation to PAHs are high
temperatures and residence time [58]. This stage of pyrolysis is
also associated with pyrolysis of D-limonene and styrene [56,59].
2.3. Tyre pyrolysis technology and the effect of operational
parameters on product composition
Commonly used pyrolysis technologies are distinguished by
the heating rate and residence time. The reactor type used can
be: fixed, moving, fluidised, spouted and vacuum types (refer to
Table 2 for detail). There are also some novel technologies, such as
microwave [60,61] and ultrasonic [62–64]. Moreover, various cat-
alysts can be applied to improve the quality of TPO, using a pro-
cess called catalytic pyrolysis [65–73]. Finally, it should be noted
that feedstock preprocessing can vary from the preparation of rub-
ber powder (required for fast heating), through centimetres-large
pieces, to pyrolysis of whole tyres [74,75]. Whole-tyre pyrolysis is
achieved using special reactors designed for both intermittent and
continuous operation [76].
The content, as well as the properties and composition of in-
dividual pyrolysates fractions, may vary upon the technology and
conditions employed during the process. The amounts of polymer
types present in rubber significantly influence the product fraction
distribution, as well as the content of different hydrocarbons such
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al. Progress in Energy and Combustion Science 85 (2021) 100915

Table 2
Type of reactors used during pyrolysis and most relevant process conditions affecting TPO yield.

Type of Reactor vol. [dm3 ] Inert gas used Process description (time) TPO Yield [%] Temp.∗ [deg C] References
reactor

fluidized bed 0.9 nitrogen + air continuous 25-38 700 Lee et al. (1995) [77]
n.a. nitrogen n.a. n.a. n.a. Williams and Besler (1995) [48]
nitrogen/steam fast pyrolysis 51-65 500 Kaminsky and Mennerich (2001) [78]
steam n.a. 30-50 450 Dai et al. (2001) [79]
various over 36 600 Kaminsky et al. (2009) [80]
nitrogen continuous, fast pyrolysis 25-45 400 Raj et al. (2013) [81]
0.23 nitrogen fast pyrolysis; catalytic n.a. n.a. Zhang et al. (2014) [82]
4.1 nitrogen continuous, fast pyrolysis 26-38 400-450 Wang and Jan (2018) [83]
n.a. hydrogen intermittent (4-60 min) 42-47 375 Mastral et al. (2000) [84]
fixed bed 1.5 helium intermittent (15 min) 30-38 550 Dıéz et al. (2004) [85]
1.2 nitrogen intermittent (60 min); catalytic 35-56 430 Williams and Brindle (2002) [65]
0.4 nitrogen intermittent (60 min); catalytic 46-60 425 Kar (2011) [70]
3.5 nitrogen intermittent (30 min) 5-39 700 De Marco Rodríguez et al. (2001) [86]
2.2 nitrogen intermittent (120 min) 30-38 500 Choi et al. (2014) [87]
0.59 nitrogen intermittent (60 min) 47-56 n.a. Ucar et al. (2005) [88]
0.95 nitrogen intermittent (120 min) 30-43 500 Berrueco et al. (2005) [51]
0,004 nitrogen intermittent (15 min) 36-45 n.a. Murillo et al. (2006) [89]
2.1 nitrogen intermittent (50 min) up to 49 475 Islam et al. (2008) [90]
0.08 n.a. intermittent 20-58 n.a. Acevedo et al. (2013) [91]
1.7 nitrogen n.a. 33-41 Choi et al. (2013) [92]
6.7 nitrogen intermittent (160 min) 38-88 Al Mamun al. (2016) [93]
n.a. nitrogen intermittent (20 min) 41-53 450 Hopa et al. (2017) [94]
2.8 n.a. intermittent (16 min) 25-55 n.a. Odejobi et al. (2020) [95]
179 nitrogen intermittent 30-42 400 Aziz et al. (2018) [96]
0.5 nitrogen intermittent 45-65 400 Kumar Singh et al. (2018) [10]
moving bed 0.15 nitrogen continuous (240 min) 54 n.a. Aylón et al. (2008) [97]
n.a. nitrogen continuous 28-48 Aylón et al. (2010) [98]
Vacuum 0.1 -4 kPa vacuum intermittent 33-50 480 Zhang et al. (2008) [69]
n.a. -3 kPa vacuum intermittent 10-55 415 Roy et al. (1990) [99]
848 -13 kPa vacuum continuous 50 n.a. Benallal et al. (1995) [100]
848 -80 kPa vacuum continuous n.a. Chaala and Roy (1996) [101]
n.a. -70 kPa vacuum intermittent Roy et al. (1997) [102]
848 -10 kPa vacuum n.a. 43-56 Roy et al. (1999) [103]
n.a. n.a. 30-53 Rombaldo et al. (2008) [104]
n.a. Vihar et al. (2015) [105]
40640 intermittent 40-45 Tudu et al. (2016) [106]
not specified n.a. nitrogen intermittent (30 min) 18-56 550-575 González et al. (2001) [107]
helium n.a. n.a. n.a. Seidelt et al. (2006) [52]
nitrogen intermittent (60 min); catalytic ˜
Dung et al. (2009) [108]
nitrogen intermittent (180 min) 28-41 400 Czajczyńska et al. (2020) [109]
spouted bed 11.2 n.a. continuous (30 min) 44-55 n.a. López et al. (2010) [110]
reactor n.a. continuous (50 min) 54-58 Alvarez et al. (2017) [58]
28.3 intermittent; catalytic 40 Ayanoğlu and Yumrutaş (2016) [71]
0.16 hydrogen intermittent (90 min); catalytic 10-37 550 Ramirez-Canon et al. (2018) [111]
rotary (auger) n.a. nitrogen continuous (80 min) 39-51 n.a. Choi et al. (2016) [112]
reactor n.a. n.a. n.a. Martínez et al. (2014) [113]
∗
Temperature for optimum TPO yield.Reactor Type

as aromatics and olefins, in gas and liquid fractions. This section
gathers the state of the art in tyre pyrolysis technology and the
knowledge of how different pyrolysis parameters influence the fi-
nal product yield. The most relevant data is illustrated in Table 2.
Note that a more extensive yet visually less impactful version of
this table is included as Appendix 1. The tabularised data is fur-
ther followed by a factor-by factor discussion. The focus is on max-
imising the yield of TPO, as this fraction is central to the present
review. The previous section summarising the mechanisms of py-
rolysis underpins the following discussion.
Table 2 presents an overview of generic types of reactors used
for ELT pyrolysis. Additionally, maximum TPO yields achieved by
different authors and key process parameters are provided. Note
that there are a few comprehensive reviews of ELTs pyrolysis tech-
nologies. Therefore, our review covers only the most important
technological findings, focusing instead on properties of the py-
rolytic products and their engine application.
Martínez et al. [114] differentiated between slow and fast py-
rolysis, which are distinguished by heating rate and vapour resi-
dence time. Generally, fixed-bed reactors and larger material parti-
cles normally are used for slow pyrolysis, which runs at lower tem-
peratures and takes minutes to hours. Rotary kiln and fluidised bed
reactors are the main types for fast processes, which are distin-
guished by small material particles, fast heating rates and vapour
residence times no longer than a few seconds. Czajczyńska et al.
[44] also compared different types of reactors while differentiat-
ing between slow and fast pyrolysis, but with the focus on gas
yield. The main conclusion was that fast pyrolysis yields more liq-
uid fraction, due to avoided secondary reactions, whereas the main
product of slow pyrolysis is a solid fraction. This statement is ob-
viously a simplification since the actual yield depends heavily on
process conditions. Nevertheless, it qualitatively illustrates the gen-
eral trend.
Another review by Lewandowski et al. [76] confirms this the-
sis by comparing results from different reactors. A more thorough
analysis of pyrolysis product composition related to reactor type is
depicted in Fig. 4, summarising results obtained using different re-
actors, but at roughly the same process temperature of 500°C. It is
evident from Fig. 4 that fluidised bed reactors provide maximisa-
tion of the TPO yield. Attainable TPO production efficiency for fixed
bed and mechanically mixed reactors is approximately 10% lower.
At this point, it should be emphasised that other process param-

8
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 4. Product lumps in different types of reactors [76]. Reproduced with permis-
sion from Journal of Analytical and Applied Pyrolysis, Elsevier.
eters, e.g. heating rate, feedstock, particle size etc. affect the TPO
yield to a large extent. The reported results are obtained on large
capacity, pilot-scale or model (laboratory-scale) installations. Addi-
tionally, liquid fractions can be condensed at various temperatures
and the yield analysis can be made on a wet or dry basis. Nev-
ertheless, the following paragraphs aim to describe the individual
parameter effects.
2.3.1. Temperature
One of the most significant factors affecting pyrolysis is the
temperature at which the process is performed. Therefore, the ma-
jority of the research has focused on process efficiency, with tem-
perature being one of the most important parameters in this en-
deavour. From the perspective of valorisation of pyrolysis product
streams, maximum process efficiency coincides with maximising
the quantity and the heating value of the liquid fraction.
The existence of a distinct extremum (maximum) in TPO yield
with pyrolysis temperature was noted by many researchers, includ-
˜
ing: Murillo et al. [89], Rombaldo et al. [104], Dung et al. [108],
Pradhan and Singh [50] and Luo and Feng [115]. Pradhan and Singh
[50] reported high TPO yield in a laboratory-scale batch reactor
fed with scrapped bicycle tyres in 10 mm chunks. The peak TPO
conversion (49.6%) was reported at 600°C, a considerably higher
temperature than in the other referred works by Berrueco et al.
[51], de Marco Rodríguez et al. [86], Laresgoiti et al. [116,117] and
Aydın and İlkılıç [118]. The temperature dependency of TPO yield
was explained, following Islam et al. [90] (originally referring to
Cunliffe and Williams [119]), by strong cracking of tyre rubber dur-
ing second-stage reactions in the mid-temperature range (refer to
Fig. 3). The insensitivity of TPO yield to temperature beyond the
maximum yield point, following González et al. [107] and Nisar
et al. [120], can be explained with the observation that the liquid
fraction was subsequently cracked to a gaseous fraction. This was
further attributed to the rapid extraction of generated products
from the autoclave. Results presented by González et al. [107], and
Dai et al. [79] also indicated that peak TPO yields were reached
at a certain temperature (respectively, 55.6% at 550°C and approx-
imately 50% at 450°C). Further increases in temperature (explored
range up to 70 0 and 80 0°C respectively) led to a reduction in oil
fraction. This was correlated with the increase of the gaseous frac-
tion yield.
9
Progress in Energy and Combustion Science 85 (2021) 100915
Note that a handful of studies report TPO yield saturation at
certain temperature levels. Berrueco et al. [51] carried out pyrolysis
of waste tyres in an atmospheric-bed batch reactor at temperatures
between 300°C and 700°C. There was a lack of sensitivity in TPO
yield below 400°C but yield was observed to gradually increase as
the temperature rose from 400°C, reaching a maximum at 500°C.
Further temperature increase did not affect pyrolysates yields. Sim-
ilar results were presented by de Marco Rodríguez et al. [86], con-
ducting pyrolysis at a wide range of temperatures (30 0, 40 0, 50 0,
60 0 and 70 0°C) in a nitrogen atmosphere. The cited authors ob-
served that a significant yield increase occurred at 30 0-50 0°C and
peaked at 500°C (38.0%). The yield remained at a similar level at
temperatures above 500°C. The same tendency was noticed for the
gaseous fraction. Laresgoiti et al. [117] carried out pyrolysis in iden-
tical conditions to de Marco Rodríguez et al. [86] and presented the
same results. Laresgoiti et al. [116] observed the same tendency in
earlier work too. Aydın and İlkılıç [118] also noticed that the max-
imum TPO yield (40%) was achieved at 500°C and that it remained
at a similar level as the temperature was increased to 750°C. How-
ever, the cited authors observed no correlation between gases and
oil fractions formation, contrary to the results of previous works.
The third general trend implies that TPO yield diminishes with
increasing temperature. This was reported by Williams and Brindle
[65], Galvagno et al. [121], Mastral et al. [122] and Aylón et al. [98].
Aylón et al. [98] conducted nitrogen atmosphere pyrolysis at 600,
70 0 and 80 0°C. They observed that as the temperature rose there
was a significant decrease in TPO yield fraction, an increase of gas
fraction and a relatively constant solid yield. The decrease of the
oil fraction and an increase of gases were explained by the cracking
of liquids. The same tendency was found by Galvagno et al. [121],
who examined three pyrolysis temperatures: 550, 600 and 680°C.
The highest TPO yield (38.12%) occurred at 550°C while the lowest
(31.82%) was at 680°C. The gas fraction yield increased from 2.39%
at the lowest pyrolysis temperature to 10.75% at the highest.
For a great number of works, presented in Table 2 the limited
range of temperature sweeps performed makes it difficult to de-
termine with absolute certainty whether saturation or change in
monotony determined TPO yield as pyrolysis temperature rose. Fig-
ure 5 visualises the discrepancies already mentioned between in-
dividual results. Despite these discrepancies, some qualitative con-
clusions can be drawn from Fig. 5 and the above paragraphs. The
results indicate that there is a temperature window between 400°C
and 800°C in which TPO production is maximised. However, based
on different TGA curves, e.g. [50,70,123,124] the pyrolysis process
should be completed below 550°C. This is because the pyrolysis is
not static, so the effects of temperature on TPO yield from a given
feedstock can be thoroughly analysed only, if at minimum, heating
rate, heat transfer in the pyrolysed material and gas retention time
are taken into consideration [125]. The first two factors determine
the feedstock decomposition, while the third determines secondary
cracking of the pyrolisates, which produces gas at the expense of
TPO. Therefore, apparently contradictory effects of temperature, in
fact, can lead to coherent conclusions. Another important issue is
the location of temperature measurement. In the case of contin-
uous processes, usually final temperature is provided, whereas in
the case of an intermittent process there is a wide-span tempera-
ture stratification.
2.3.2. Feedstock size and heating rate
While scoping Table A1 it becomes evident that, due to the
kinetic character of the process, the size of the tyre shred influ-
ences pyrolysis efficiency, and hence TPO yield. More extensively
meshed feed material (mesh of millimetres) promotes heat en-
trainment during the process. This is especially the case when re-
actor design can take advantage of the particle size – e.g. a flu-
idised bed reactor [78]. The most suitable size of the feeding ma-
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 5. The effects of temperature on liquid fraction yield. The measurement points
are adopted from [10,11,51,58,65,79,81,88,94,126] and fitted with quadratic func-
tions for different types of reactors. The points surrounded with circles refer to
truck tyres.
terial in terms of TPO production are shreds between 1.5 and 30
mm, while sub-millimetre particles (tyre ground) promote the pro-
duction of gaseous products [58,59,70,77,78,87,88,92,97].
Scale of production is a significant aspect to consider when
specifying the feed material structure. Note that most of the re-
liable data on the influence of tyre meshing on pyrolysis that leads
to the above-mentioned generalisation comes from laboratory-
scale reactors operating intermittently. The optimal feed material
granulation may vary when scaling-up the reactor size or shift-
ing to continuous operation [96,103,106]. Furthermore, the opti-
mum heating rate for TPO production will be largely dependent
on the fragmentation of the feed material. Haydary et al. [123],
using a screw-type flow reactor performed programmed experi-
ments, supported by the heat transfer model, to find correlations
between heating rate and particle size. The comparison of mate-
rial conversion rates for rubber particles from 4 mm to 8 mm
showed that at the pyrolysis temperature of 550°C, the time re-
quired for 90% conversion was 25 and 95 seconds, respectively.
Mkhize et al. [124] analysed the effects of the temperature and
heating rate on TPO yields, using a fixed-bed, slow pyrolysis re-
actor with a nitrogen atmosphere. They established for individual
temperatures (309, 350, 450, 550, 591°C) that the maximum oil
fraction yield varied greatly depending on the heating rate (0.86,
5, 15, 25, 29.14°C/min). Generally, the best results (around 45% oil
mass fraction yield) were achieved in medium ranges of tempera-
tures and heating rates. Similarly, other authors usually claim that
heating rate is a relevant control parameter yet fail to deliver clean
sweeps of heating rate undisturbed by variations of other parame-
ters. Thus, we believe currently it is impossible to draw any mean-
ingful conclusions on the effect of heating rate, so we leave this as
one of the knowledge gaps for further works to cover.
2.3.3. Inert gases and catalysts
The atmosphere (the injection of gases or vapour) is an impor-
tant variable during pyrolysis. The flow of the inert gas stabilises
and equalises the temperature inside the reactor. In the case
of the fluidised-bed reactor, this also aims to provide a more
homogeneous temperature distribution in the bed. Nitrogen and
helium are frequently used to replace atmospheric air during
10
Progress in Energy and Combustion Science 85 (2021) 100915
pyrolysis (refer to Table 2). The gases hinder the generation of
oxides and limit the partial pressures of substrates. They also act
as carriers of volatile products of the process, while reducing the
condensation rate of aromatics and supporting carbon-black bind-
ing. Ramirez-Canon et al. [111] and Kan et al. [127], independently
presented that better quality TPO can be obtained by the use of
hydrogen as an inert gas. Hydrogenative pyrolysis stabilises the
hydrocarbon chains by hindering the re-polymerisation process.
It is also proven to remove sulphur from the liquid fraction (see
Section 3.3 for details).
Excluding the synergistic effect of hydrogen which is reactive
in the conditions of pyrolysis, for other inert gases, the vapours
retention time (practically regulated by the gas flow rate) is the
dominant factor influencing yield of liquid and gaseous fractions.
Shorter retention times support high yield of liquid products; pro-
longed presence of vapours inside the reactor leads to reactions
promoting gaseous products [79,80].
The use of a catalyst is usually designed to enhance the qual-
ity of a particular fraction. In general, catalytic pyrolysis is per-
formed to achieve monoaromatic compounds like benzene, toluene
or xylene [128]. On the other hand, catalysts may also reduce the
quantity of undesirable components (such as polycyclic aromatic
hydrocarbons) in the final product. Typical catalysts are copper ni-
trate, ZSM-5 zeolite, magnesium oxide (MgO), calcium carbonate
(CaCO3 ), sodium hydroxide (NaOH), sodium carbonate (NaCO3 ), ze-
olite and activated alumina. The efficiency of the catalysts depends
on the size of the pores: microporous catalysts are among those
offering the highest efficiency. Such structures are, however, more
prone to clogging by post-pyrolysis vapours, leading to deactivation
of the catalyst [65,70,82,108,128].
Williams and Brindle [65] conducted pyrolysis using Y-zeolite
(CBV-400) and ZSM-5 catalysts. While examining the effect of dif-
ferent catalyst bed temperatures (40 0-60 0°C, at 50°C increments)
they found the highest TPO yield (40% and 45% for each catalyst
respectively) in the temperature range of 425-475°C. Further in-
creases in temperature increased gaseous fraction production but
reduced the oil fraction: it was approximately 33% at 600°C for
both catalysts. It is worth noting that in the cited work, pyrolysis
was also conducted without the catalyst, which actually resulted in
higher TPO yield (55.8% at 500°C). This trend was also confirmed
by other researchers [128] and the high-level conclusion is that
the increase of the temperature of a catalyst bed causes increased
production of the gaseous products, at the expense of the liquid
fraction.
2.3.4. Feedstock type
The influence of different categories of tyre feedstock has been
studied by many researchers. A handful of published comparative
analyses leads to a common conclusion that the type of feedstock
(e.g. car or truck tyre) affects TPO yield, due to differences in their
proportions of natural rubber and synthetic rubbers.
A cohesive view of this issue can be formulated when assess-
ing data from two works. Fig. 6 combines the results of Ucar et al.
[88] and Kumar Singh et al. [10]. Both studies used different cat-
egories of waste tyres at similar pyrolysis temperature ranges, but
with different reactors: fixed-bed and stirred tank respectively. In-
terestingly, both studies show consistent trends in terms of TPO
yield and feedstock categories. Independently of process conditions
and reactor type, heavy-duty tyres yielded significantly higher liq-
uid fraction compared to the light-duty tyre feedstock. The latter
yields high amounts of char. Material analyses of the feedstock
composition consistently showed that truck tyres have a higher
content of natural rubber and a lower fraction of synthetic rub-
ber when compared to passenger car tyres. Additionally, Ucar et al.
[88] pointed out that truck tyres used SBR as a synthetic compo-
nent, whereas car tyres contained mainly BR.
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al. Progress in Energy and Combustion Science 85 (2021) 100915

Fig. 6. Product distributions from pyrolysis of scrap tyres; data elaborated based on Ucar et al. [88] and Kumar Singh et al. [10]. The exact numbers can slightly differ than
presented in original research papers, because the data were converted to the dry basis.

Kumar Singh et al. [10] used TGA to study the interaction of

different categories of waste tyres during pyrolysis. Higher frac-
tions of natural rubber (predominant in heavy-duty vehicle tyres)
was reported to reduce the degradation temperature, while syn-
thetic rubber from car tyres had an opposite effect. Importantly, a
synergistic effect was noted from interactions of both rubber frac-
tions, so solid and gaseous fraction yields were reported respec-
tively higher and lower for co-pyrolysis than predicted from indi-
vidual fractions pyrolysis data. However, the TPO yield showed a
much lower synergistic effect. More information on co-pyrolysis of
waste tyres with other materials follows in the next subsection.

2.3.5. Co-pyrolysis of tyres with other materials

As mentioned in the introduction, one particular benefit of the
pyrolysis process is its flexibility on feedstock. Some aspects of co-
pyrolysis of waste tyres with other materials deserve particular at-
tention because there seems to be an added value of material in-
teraction for improving TPO composition and yield.
Almost all available studies of co-pyrolysis focus on biomass as
the primary feedstock, and examine the large oxygenates content
of bio-oils, leading to corrosion problems, the low calorific value of
the end fuel and its instability [129]. The co-pyrolysis of biomass
and low oxygen content / high calorific value polymers provides
effective mitigation to the above issue [113].
The publications to date in this area focus on the co-processing
of biomass and plastics: there are fewer studies of co-pyrolysis of
biomass and scrap tyres. Abnisa and Wan Daud [130] studied co-
pyrolysis of palm shells and scrap tyres, changing the process tem-
perature, time and mixing ratio. They showed that co-processing
can improve the yield and quality of crude oil while compensat-
ing for the shortages of biomass in fuel production. Farooq et al.
[131] conducted experiments with wheat straw and waste tyres
and found that, compared to oil derived from neat biomass, the
co-pyrolysis product was more stable with significantly lower alde-
hyde content. Chen et al. [5] were the first to explain this syn-
ergistic effects by investigating the kinetics of biomass (tobacco
stalk) and scrap tyre co-pyrolysis. According to the authors, the
alkyl groups largely present amongst tyre decomposition products
can interact with carbonyl groups in tobacco stalks and lower the
CO2 production of the pyrolysis. This increases the oil fraction yield
and lowers the energy input of the whole process.
Ultimately, the study of Chen et al. [5] is the only one that
brings forward the primary role of waste tyres in the co-pyrolysis.
Contrary to earlier mentioned studies [130] and [131], the authors
explored tyre/biomass ratios above 1:1. They investigated seven
different feedstock compositions, equally distributed between the
100% tobacco stalk and 100% tyre scrap references. Importantly for
the prospect of waste tyre as feedstock, the authors reported the
greatest synergistic benefits for co-pyrolysis (tyre/biomass) frac-
Fig. 7. Sankey diagram for tyre pyrolysis at 500°C. Averaged values for HHV and
yields based on data gathered in Section 2.
tions of 4:6 with over 30% reduction in activation energy with re-
spect to the 100% biomass reference.
Bearing in mind the lack of studies concerning co-pyrolysis
with waste tyre as the primary feedstock and the promising ini-
tial results by Chen et al. [5], it appears that TPO production has
still some uncharted improvement potential.
2.4. TPO production efficiency and life cycle analysis
2.4.1. TPO energy and exergy efficiency
The energy density of waste tyres is estimated at around 31.4
MJ/kg, which is roughly double that of mixed biomass [40,132].
In terms of energy efficiency it is sufficient to say that when
optimised for oil production, tyre pyrolysis can be self-sustainable,
with only around 9.5% of total tyre energy used to power the
process and with only around 2% of total energy released to
the ambient surroundings [133]. The rest of the products can be
properly valorised. The process Sankey diagram (Fig. 7) show-
ing the energy flow uses averaged heating values and yields of
the individual fractions, garnered from the detailed review in
Sections 2.3 and 2.5. Fig. 7 is considered self-explanatory and left
without detailed comments.
More recent studies related to TPO production efficiency are
based on exergy analysis, which quantifies the process capability
to recover the energy and its losses related to irreversibility. Al-
tayeb et al. [134] calculated the exergetic efficiency of the pyroly-
sis process, based on a detail analysis of chemical exergy of sub-

11
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
trates and products. The overall exergetic efficiency of the rotary
kiln reactor was found to be 69.9%, which is equivalent to an ex-
ergy destruction of 30.1% due to process irreversibility. Notably, the
authors indicated there is almost no further potential for efficiency
improvement with change of reactor or process conditions.
The obtained exergy efficiency is comparable to the value com-
monly reported for gasification plants (roughly 70%) [135]. For
reference, the exergy efficiency of transesterification to obtain
biodiesel from different feedstock is estimated to be significantly
higher, at around 80% [136]. Note, however, that in the works re-
lated to FAME, exergy losses of methanol production are not in-
cluded, so the number does not represent the complete feedstock-
product chain as with ELTs.
2.4.2. Tyre pyrolytic plant life cycle analysis and total cost of
ownership
The mentioned work of Altayeb et al. [134] is ultimately one
of the few attempting to cover the complete life cycle analysis
(LCA) of TPO production. This study, based on the simulated rotary
kiln reactor adjusted for optimal TPO yield temperature (∼500°C),
was made using dedicated software (SimaPro) and taking the geo-
economical perspective of Saudi Arabia. The system boundaries
included waste tyre transport, shredding, pyrolysis, TPO recov-
ery, distribution and end-use. The analysis also took into account
the emissions and costs related to the transport of valorised off-
streams (steel and char). The authors analysed a set of scenar-
ios in diversifying the feedstock-product routes and reactor pow-
ering scenarios, distinguishing over 20 environmental impact cat-
egories while diversifying the contribution of individual TPO pro-
duction stages. However, it did not perform a comparative analysis
with other TPO processing technologies. Nor did it provide any ref-
erence to other alternative fuel production processes. Crucially, it
presented results in a normalised form instead of revealing abso-
lute values of the individual outcomes. These are important short-
comings in the context of the ongoing GHG-impact discussion of
individual fuel/waste management options. Nevertheless, there is
one conclusion that is valuable to note. In the most feasible sce-
nario, where all non-condensable gases are used to power the re-
actor (as in the diagram in Fig. 7), the total normalised GHG impact
(CO2 and CH4 accounted) of TPO lifecycle was negligible compared
to toxic emissions. Toxic emissions in the study were divided into
several impact categories related to air/water/terrestrial toxicity
but all relating to CO, NOX , PM and waste metals were combined.
The highest-emitting process here was the combustion of the non-
condensable gases to power the reactor. These formed over 70%
of the total TPO toxic emission-related impact and ultimately over
65% of the total environmental impact of TPO production. Next was
TPO end-combustion, accounting for roughly 20% and 17% impact
on toxicity and total environmental impact respectively.
A similar study, using similar methodology was carried from a
perspective of Thailand by Buadit et al. [137]. This uses the same
software for LCA with similar impacts yet excludes transport of
materials and final combustion of TPO, focusing purely on the py-
rolysis process itself. This study, however, evaluates the environ-
mental impacts of waste tyre pyrolysis both with and without ac-
counting for material recovery from avoided products. Under the
second assumption, on a problem-oriented level, three impact cat-
egories - global warming, terrestrial ecotoxicity and fossil resource
scarcity - result in negative impacts. At a damage level, similar to
Altayeb et al. [134], human health emerges as the dominant cate-
gory, resulting mainly from fine particulate matter formation from
the combustion of the gaseous fraction that powers the reactor.
As one can note from the above two paragraphs, the LCA
results heavily depend on the assumptions that are made and
the geo-socio-economical perspective. Thus, the most relevant
arguments for TPO feasibility come from a comparative analysis
12
Progress in Energy and Combustion Science 85 (2021) 100915
Fig. 8. Comparison of net benefits (10 years depreciation period and total impact)
for the four ELT treatment technologies in China. Merged data from Li et al. [138].
of pyrolysis with other tyre processing technologies and TPO with
other fuel alternatives. We have not found any reliable studies
comparing TPO LCA with that of other alternative fuels. Only
Li et al. [138] have assessed pyrolysis together with other ELT
treatment technologies. This Chinese case study is ultimately by
far the most thorough and accurate analysis available on TPO
LCA. It accommodates similar system boundaries as the study of
Buadit et al. [137], from feedstock to products, excluding transport,
and accounts for material recovery from avoided products. For
example, 350 kg of crude TPO yielding from 10 0 0 kg of scrap
tyres is assumed to substitute 175 kg of diesel fuel. Under the
same boundaries, LCA extended over economic analysis is applied
to four processes currently used in China to process waste tyres.
These four processes are ambient grinding (producing crumb
rubber to be used mainly in construction); active de-vulcanisation
(currently the dominant processing technology in China); py-
rolysis; and Illegal oil extraction. The last process is analogous
to pyrolysis but performed without proper equipment, emission
control and without recovering the off-gases and other substances,
which are instead illegally dumped. This illegal practice with its
high environmental impact currently handles over 14% of ELTs in
China. The end results of the LCA and environmental–economic
analysis performed by Li et al. [138] are depicted in Fig. 8.
According to these results, pyrolysis is the best ELT processing
technology in terms of cumulative GHG reduction and second-best
in terms of fossil fuel substitution. In the second category, it is sur-
passed by devulcanization, the main route for ELTs in China. Py-
rolysis, however, does not pose the same excessive impact on hu-
man health as devulcanisation. However, it is necessary to point
out at that at the time of the study (2010), the problem of air-
borne pollution in China was regarded as more pronounced than
the impact of GHG. This was recognized by Li et al. [138] because
the weighting factor of all respiratory categories was double com-
pared to climate change. If applying the same approach with the
current constraints that attach greater value to CO2 reduction, the
weighted eco-indicators points in Fig. 8 would further reinforce the
position of tyre pyrolysis as environmentally feasible technology.
Still, in the framework of the discussed study, according to Fig. 8,
pyrolysis scores best in overall environmental impact and at the
same time is considered the most economically feasible ELT man-
agement technology. Over a 10-year depreciation period, the net
benefit of a new pyrolysis plant in China (2500 tonnes/year ca-
pacity) would be 32% higher compared to the current devulcani-
sation facility with similar capacity. Note that in this study the as-
sumed plant capacities are rather small because they are intended
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al. Progress in Energy and Combustion Science 85 (2021) 100915

Table 3
The current market price of most common fuel alternatives including TPO. Prices exclude value added or fuel related taxes and are averaged over the period indicated in the
date column.

Fuel category Price [$/1000 kg] Remarks Date Reference

RME 1049 Rapeseed methyl ester (RME) according to RED scheme with Nov. Greenea (Hillairet and
quality EN 14214, water 350 ppm, CFPP 11°C, sulphur max 12 2020 Madiot [140])
ppm, FOB ARA
TME 1040 Tallow methyl ester (TME) according to RED scheme with quality
EN 14214, water 350 ppm, CFPP 11°C, sulphur max 12 ppm, FOB
ARA
UCOME 1198 Used cooking oil methyl ester (UCOME) according to RED
schemes with GHG saving >90% with quality EN 14214, water
350 ppm, CFPP 0°C FOB ARAD
UCO 730 Used cooking oil (UCO) according RED schemes with FFA max 5%,
Water & Impurities max 2%, Sulfur max 40 ppm, IV min 70-80
Tallow cat. 1 520 Animal fat cat. 1 produced under the terms of the Regulation
(EC) No. 1069/2009 – method 1) with FFA max 20%, impurities
0.15%, water max 0.6%
SVO rapeseed 950 Straight vegetable oil for fuel applications according to DIN Nov. NESTE [141]
51605 European Rapeseed oil reference (Crude Dutch /EU) 2020
SVO palm 730 Straight vegetable oil - Malaysian palm oil / Rotterdam (NL)
TPO 350 No quality standards exist, price depends on the quality and Mar. 2019 DOING Holdings [142]
varies from country to country (Americas 342-404 $/1000 kg; EU
326-349 $/1000 kg; Asia 355-379 $/1000 kg)
GASOIL 420 European low sulfur gasoil, large market variations ± 47%; Nov. 2020 Focus Econ. [143]

for decentralised applications. The only relevant data related to the

economical feasibility of large tyre pyrolysis plants (100 tonnes/h
capacity) come from 1999. This legacy work of Shelley and El-
Halwagi [139] assessing tyre pyrolysis plant economics in UK con-
ditions suggested, for an optimised scenario, a total investment
cost of 18 million euros, with a fairly good return of investment
rate of 18%. The authors, however, assumed hydrotreatment of
crude TPO as part of the process, revalorising ready fuel compo-
nents. The cited studies are therefore not comparable, neither in
time nor socio-geographical conditions. Consequently, we consider
the current state of the art in pyrolysis economics is still uncertain.
As a final note on tyre pyrolysis economics, we must mention
that while performing this review we have come across several re-
cent publications on this topic which showed severe errors in their
principal assumptions. These include, for example, overestimating
TPO value by an order of magnitude, thus making claimed con-
clusions unfeasible. These studies were deliberately excluded from
Fig. 9. Comparison of specific CO2 emissions from the production of different fuel
this review in order to avoid their corrupting influence. We will alternatives. Biodiesel values reproduced from [144]. Value of TPO calculated based
return to the bigger issue of reliability of the information on TPO on the assumptions discussed in the text.
in Section 5.

2.4.3. TPO vs other fuels - remarks on the economics and GHG
footprint
In the light of the evident lack of comparative LCA of TPO
with other fuel alternatives, we conclude this section with a brief,
absolute value-based discussion of selected GHG and economic
factors directly relevant to the issue of fuel feasibility. To this
end, Table 3 collates available information about current market
prices of different fuel alternatives. It is not the goal of the present
work to discuss the global trends in fuel markets: the main point
from Table 3 is that TPO currently has the lowest market price
of all available options. The price of TPO (excluding value-added
tax or fuel duty) is comparable with that of fossil gasoil and is
over 50% lower than the cheapest large–scale, straight vegetable
oil, palm oil. This, coupled with the fact that unlike all other bio
components, TPOś price did not significantly change during the
past 10 years, shows there is still only minor interest in the fuel
industry for using this as a fuel component for further refining.
On the upside, there is potential to accommodate TPO directly as
engine fuel in transport sectors (such as marine) which cannot
afford expensive fuels.
A comparison of the direct CO2 footprints of different alterna-
tive fuels (Fig. 9) reveals another incentive for TPO compared to
first-generation biofuels. This figure does not assume any product
valorisation of removed CO2 due to product substitution.
Tyres as waste are commonly counted as zero-CO2 feed-
stock. The CO2 emission for TPO accounts mainly for burning
the non-condensable gases to power the reactor (including de-
moisturisation of the feedstock). This is commonly reported for
tyre pyrolysis at a level of 68.06 (kg/tonne waste tyres) [137,145].
Energy consumption and so hence also the CO2 footprint related
to ELT transport, pre-processing (grinding, mechanical separation)
and end product valorisation (extraction, transportation to end-
users) is usually assumed at a level of 15-19% of the pyrolysis
process, depending on scenario [134,137,139]. Assuming TPO yields
reported for the state-of-the-art reactors at the level of 45-55%
(refer to Table 2) and lower heating values of 40 – 42 MJ/ kg (refer
to Table 6), the final TPO well-to-tank emissions are on average
3.76 g CO2 e/MJ.
In the case of SVOs and FAME, assuming they are still produced
mainly from first-generation feedstock, it is large CO2 footprint of
farming activities (mainly fertilisers) that is responsible for the vast
amount of their well-to-tank CO2 emissions. This is not the case for
biofuels derived from waste, non-edible by-products (see Table 3 –
tallow cat 1) or waste cooking oil. Note that tallow biodiesel,

13
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
however, is characterised by its large energy demand to extract oil
from fat, entailing boiling and mechanical separation [144].
As shown in Fig. 9, TPO production has roughly the same car-
bon footprint as oil extraction for rapeseed and soy (3.12 and 4.04
g CO2 e/MJ respectively) and is comfortably superior to any first-
generation FAME or SVO in the overall balance. Note that CO2
emissions of soy and canola SVOs can be derived directly from
Fig. 9 by neglecting the biodiesel combustion contribution. Further,
note that the currently most economically viable palm oil (Table 3)
is considered the worst in terms of CO2 footprint [146].
As a final point, it is apparent that the price of all the men-
tioned bio components relates to their opportunity to provide GHG
reduction. This leads to the current bizarre situation in which used
cooking oils (UCO) and their esters (UCOME) have greater market
value than their un-used originates. There is definitely a value in
the green image for fuel companies.
Having said that, we acknowledge that a detailed GHG emis-
sions life cycle analysis for both fuel categories, TPO and bio-oils,
is extremely complex and heavily dependent on geo-economic fac-
tors or even fundamental assumptions. Consequently, the results
presented in Fig. 9 should be treated as indicative. Qualitatively,
however the differences are evident, and in the context of the
above discussion, TPO can be considered more favourable in terms
of CO2 footprint than all first-generation biofuels, and is ultimately
the cheapest alternative.
2.5. General characterisation of pyrolysates
2.5.1. Solid fraction
The solid fraction is made up of hydrocarbons with more than
10 carbon atoms and consists of aromatics, non-aromatics and in-
gredients containing sulphur, nitrogen and oxygen [147]. Analysing
the elemental composition of solid fraction, de Marco Rodríguez
et al. [86] found that it was predominantly carbon, accounting
for approximately 83% by weight. The share of other elements
was significantly lower. Hydrogen was 2.4%wt. at 400°C and ap-
prox. 0.6%wt. at 50 0, 60 0, 70 0°C. Nitrogen was approx. 0.3%wt.,
sulphur was approx. 2.4%wt. Oxygen and others accounted for
approximately 1%wt. The cited authors also found that the ob-
tained pyrolytic residues were characterised by the concentration
of ash (from 9.0 to 13.2%wt.), far higher than for commercial car-
bon black, which has an admissible concentration of no more than
0.5%wt. The ash in the pyrolytic residues comes from the original
tyre inorganic fillers. López et al. [148] presented that tyre rub-
ber ashes consisted of SiO2 (52%wt.), ZnO (27%wt.), Na2 O (8.6%wt.),
CaO (4.6%wt.), Al2 O3 (2.8%wt.). The concentrations of MgO, P2 O5 ,
K2 O, Fe2 O3 and TiO2 were between 0.4%wt. and 0.9%wt.
The solid fraction obtained by tyre pyrolysis can be used as
a solid fuel [149], a carbon black for rubber manufacturing [86],
a filler in road bitumen [150–152] or an adsorbent material. For
the latter application, however, the carbon residue requires activa-
tion, which may be accomplished by either physical or chemical
methods [9,153–155]. Physical activation is conducted by partial
gasification using steam or CO2 as activating agents [153,154,156].
Chemical activation entails treating the char with nitric acid, hy-
drogen peroxide, ammonium persulfate or impregnated by potas-
sium hydroxide and phosphoric acid: these act as a dehydrated ac-
tivating agent [9,155].
2.5.2. Gaseous fraction
The gaseous compounds include H2 , CO, CO2 , CH4 ,
C2 H6 , C2 H4 and slight amounts of higher hydrocarbons
[51,65,79,107,115,121,126,148,157,158]. Table 4 provides a compre-
hensive review of gas fraction composition for different pyrolysis
temperatures. Note that the various studies use different feedstock
or types of reactors. At this point, it is worth noting that gas
14
Progress in Energy and Combustion Science 85 (2021) 100915
yield generally increases with temperature [126]. González et al.
[107] pointed out that production of hydrogen increases 10 times,
from 0.57 g/kg of scrap tyre to 5.3 g/kg, with the increase of
temperature from 400°C to 700°C. Across the same temperature
range, production of methane went from 2 g/kg to 79 g/kg. Pro-
duction of ethylene and ethane rose from 0 to 128 g/kg and 31
g/kg respectively. Production of CO and CO2 was not differentiated
by temperature to any great extent. The increase in hydrogen and
hydrocarbons production at nearly constant CO and CO2 yield
resulted in higher gas calorific value, rising from 12 MJ/Nm3 , (the
value of pure CO) to 42.9 MJ/Nm3 , which is typical for natural gas.
Analysis of Table 4 reveals that different process parameters
provide significantly different pyrolytic gas compositions for sim-
ilar temperatures. This can be attributed to different feedstocks,
reactor types, processing times and heating rates. What is more
meaningful is that the different studies produced different trends.
For example, Galvagno et al. [121] observed a reduction of hy-
drogen content with temperature, whereas the fraction of CH4 in-
creased. A similar trend in H2 concentration for the same temper-
ature range was observed by Berrueco et al. [51]. However, Luo
and Feng [115] reported an increase of H2 content with a paral-
lel decrease in CH4 . It is also worth to notice that Luo and Feng
achieved H2 concentrations roughly twice as high as other studies,
attributed to the use of a catalyst. This research also extended its
range of process temperatures higher than other studies.
Dai et al. [79] systematically analysed the effects of temperature
and residence time on the composition of pyrolytic gas. The tests
were realised in a temperature range from 350°C to 800°C. For
the given temperature range, the fraction of hydrogen increased
monotonically from 1% to 15% and the fraction of CH4 increased
from 7% to 40%. The fraction of CO increased with temperature
from 1% to 7%, whereas the fraction of CO2 decreased from 8% to
2%. In general, concentrations of unsaturated hydrocarbons were
found to be higher than that of saturated, which was attributed
to double carbon bonds within the rubber molecules. Additionally,
the rise in temperature increased ethylene concentration and de-
creased ethane concentration, in the same range for both compo-
nents. Analysing the effects of residence time, it was found that,
at 600°C, an increase of residence time from one second to five
seconds increased the content of H2 , CH4 and C2 H4 . At the same
time, concentrations of CO2 and saturated hydrocarbons decreased.
This sensitivity to residence time was attributed to secondary re-
actions, including char reduction, tar cracking and shift reaction.
Similarly, Leung et al. [126] noticed that concentrations of hydro-
gen, methane and ethylene increase with residence time, followed
by the reduction of heavier hydrocarbons.
It should be emphasised that the obtained gaseous fraction is
characterised by a good calorific value (Table 4). Theoretically, af-
ter desulphurisation, it could be used for combustion engine ap-
plications, especially as a complement to natural gas or liquefied
petroleum gas in a gas network, providing large- scale availabil-
ity and infrastructure compatibility. It is customary for the gaseous
fraction to provide internal heat for the pyrolysis process itself. The
pyrolytic off-gas may cover the full energy needs of a pyrolysis
plant optimised for liquid yield [9]. Bearing that in mind, combus-
tion engine applications for pyrolytic gases will not be considered
further in this work.
2.5.3. Liquid fraction (tyre pyrolysis oil – TPO)
The oil fraction obtained as a result of tyre pyrolysis (TPO) is
composed of hydrocarbons between C5 and C20 and is generally
a mixture of alkanes, cycloalkanes, alkenes, cycloalkenes and aro-
matic compounds [80,89,103,107,108,115,147]. The exact composi-
tion depends on the type of feedstock and parameters of the pro-
cess. Fig. 10 compares liquid composition and is compiled from dif-
ferent studies (non-catalytic pyrolysis only). It can be noted that
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al. Progress in Energy and Combustion Science 85 (2021) 100915

Table 4
Basic characterisation of pyrolytic gases fraction

Temp. Basic gases fraction composition [%vol.] Calorific value

References [°C] [MJ/Nm3 ]
H2 CO CO2 CH4 C2 H 6 C2 H 4 C3 H 8 C4 H 8 H2 S

de Marco Rodríguez et al. [86] 400 n.a. 4.2 10.7 4.4 4.5 4.3 n.a. n.a. 2.6 84.0
(2001) 500 4.8 9.4 19.8 9.1 9.4 5.1 75.5
600 6.5 8.8 20 9 9.7 3.6 75.3
700 10.4 11.4 20.6 8.1 8.9 3.9 68.5
Galvagno et al. (2002) [121] 550 20.5 0.42 8.8 9.2 7.1 6.7 n.a. n.a. 3.4 22.1
600 17.2 1.1 8.6 13.6 8.2 8.2 2.6 24
680 10.5 0.1 6.4 22.8 9.5 12.3 2.05 29.1
Leung et al. (2002) [126] 800 20.7 2.6 1.8 44.5 4.4 17.3 n.a. n.a. n.a. 38.1
Kyari and Williams (2005) [157] 500 21.5 5.1 26.2 17.3 8.2 8.7 n.a. n.a. n.a. 30.3
Berrueco et al. (2005) [51] 400 2.61 1.08 1.41 1.02 0.43 0.25 n.a. n.a. n.a. n.a.
500 14.17 0.25 1.01 4.29 1.54 0.66
550 17.86 0.26 0.78 5.64 1.75 0.83
700 10.1 0.38 1.18 5.43 1.56 1.15
Luo and Feng (2017) [115] 600 19.39 18.63 17.03 18.25 7.36 n.a. n.a. 1.79 n.a. n.a.
700 22.07 17.78 13.76 14.73 11.8 1.86
800 28.18 16.02 10.26 12.69 13.54 1.41
900 32.24 10.57 8.84 17.01 12.81 1.8
1000 39.06 8.11 9.5 9.32 17.03 1
López et al. (2011) [148] 550 22.27 1.98 2.54 21.32 4.19 2.32 n.a. n.a. n.a. 68.7
Fernández et al. (2012) [158] 550 7.9 9 n.a. 9.9 5.9 n.a. n.a. n.a. 2.9 65.6
Kumar Sigh et al. (2018) [10] 650 18.4 4.6 3.1 11.7 18.9 4.6 6.7 n.a. n.a. n.a.
750 28.7 4.2 1.2 7 3.6 0.3 1.2

Fig. 10. Composition of TPO from different reactors at variable temperatures. Data from de Marco Rodríguez et al. [86], Ucar et al. [88], Debek
˛ and Walendziewski [74] and
Alvarez et al. [58]. Two-colour filling for the first five bars indicates aliphatic hydrocarbons cumulatively.

substantially different TPO compositions can be obtained, depend-
ing upon the reactor type, conditions and feedstock. It is also
evident that the effect of temperature depends on reactor type.
As a side note, the list of identified species and their classifica-
tion into particular hydrocarbon groups can differ from study to
study.
Debek
˛ and Walendziewski [74,159] performed pyrolysis at the
relatively low temperature of 400°C. The TPO produced, on a mass
basis, consisted of approximately 11.9% alkanes, 7.7% dienes, 4.5%
cycloalkanes, 3.7% cycloalkenes and 47.4% aromatic hydrocarbons.
Arabiourrutia et al. [147] found that raising the pyrolysis tempera-
ture from 425°C to 610°C increased the share of aromatics almost
three-fold. The aromatics content (unfavourable for engine appli-
cations due to their contribution to in-cylinder soot production)
reached 16.44% of the total TPO mass at the highest pyrolysis tem-
perature. But even that was three times less than aromatics con-
tent obtained by Debek˛ [159]. Simultaneously, the non-aromatic
compounds (C5 – C10 ) decreased from 30.48%wt. at 425°C to
23.7%wt. at 610°C. This increase in aromatics was associated with
a reduction in liquid fraction yield, which was mainly due to the
reduction in C10 lump. Furthermore, the cited authors noted that
the predominant aromatic compounds presented in the TPO frac-
tion obtained at 425°C were 1-methyl-4-(1-methylethnyl)-benzene,
1-methyl-4-(1-methylethyl)-benzene, 1,2,3-trimethyl-benzene, 1-
methylethenyl-benzene and styrene. These all had concentrations
above 0.5%wt.
Ucar et al. [88] compared the composition of TPO derived from
passenger car and truck tyres, processed under identical condi-
tions. They found that the TPO profile from cars is shaped in the
following order: paraffins < aromatics < olefins. The TPO profile
from heavy-duty truck tyres showed: paraffins < olefins < aro-
matics. These effects were attributed to different rubber compo-
sition. The higher content of natural rubber used in truck tyres
produced more paraffinic hydrocarbons, whereas synthetic rub-
ber present as the main component of car tyres produced more
aromatics [10,88]. Interestingly, increasing the pyrolysis temper-
ature did not affect the share of the individual types of com-
pounds. The same conclusion was drawn by Murillo et al. [89],
who carried out pyrolysis at 400°C, 500°C and 600°C. They
found that the share of aromatic compounds was approximately
73%, with the saturated ones amongst them being approximately
6-7% and polar aromatics contributing 20% at all temperature
conditions.
Research by de Marco Rodríguez et al. [86], on the other hand,
proved a strong thermal dependency for TPO composition. Simi-
lar findings were later mentioned by Arabiourrutia et al. [147] and
Choi et al. [59]. The original study by de Marco Rodríguez et al.
[86] observed that the share of aromatic compounds gradually in-

15
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al. Progress in Energy and Combustion Science 85 (2021) 100915

Table 5
Elementary analysis of TPO and reference diesel engine fuels

TPO elemental composition [%wt.]

References Temp. [°C] Experimental conditions
C H N S O + others

Luo and Feng (2017) [115] 600 pyrolysing using BF 78.65 16.97 0.39 1.71 2.37
700 (blast-furance) slag (B/T 80.55 15.45 0.58 1.28 3.14
800 ratio 1:1) 84.23 9.28 0.66 1.76 4.07
900 87.36 8.1 0.81 1.36 2.37
1000 88.47 8.03 0.97 1.23 1.3
Rada et al. (2012) [163] 400 reactor – a quartz tube 84.6 14.2 0.2 n.a. n.a.
batch
Czajczyńska et al. [109] 400 reactor – a stainless steel 85.5 8.5 1.5 1.2 n.a.
(2020) 500 tube batch 86.3 8.3 1.3 1.2
600 87.1 7.8 1.2 1.3
Aylón et al. (2010) [98] 600 reactor – a moving-bed 88.58 10.4 1.43 1.05 n.a.
700 reactor, atmosphere N2 91.00 8.17 1.39 1.12
800 90.56 7.66 1.28 0.93
Ucar et al. (2005) [88] 650 passenger car tyre 87.57 10.35 <1 1.35 n.a.
650 truck tyre 86.47 11.73 <1 0.83 n.a.
Mastral et al. (2002) [122] 450 reactor – fixed-bed reactor, 85.62 11.11 0.2 0.9 n.a.
500 atmosphere N2 85.59 11.12 0.21 0.91
550 85.67 11.08 0.19 0.89
Galvagno et al. (2002) [121] 550 reactor – a rotary kiln, 85.62 11.55 0.44 2.49 n.a.
600 atmosphere N2 87.82 9.42 0.55 2.21
680 87.35 10.01 0.65 1.99
de Marco Rodríguez [86] 300 reactor – an autoclave, 86.50 10.7 0.3 1 1.4
et al. (2001) 400 atmosphere N2 85.90 10.6 0.3 1.1 2
500 85.60 10.1 0.4 1.4 2.5
600 86.20 10.2 0.4 1.2 2.1
700 86 10.2 0.4 1.2 2.2
Roy et al. (1999) [103] 520 vacuum pyrolysis, 86.5 10.8 0.50 2.20 0.67
passenger car tyres
500 vacuum pyrolysis, 87.6 10.50 0.40 1.50 0.69
passenger car tyres with
silica filler
485 vacuum pyrolysis, truck 87.9 11.2 0.70 0.20 0.65
tyres
Diesel elemental composition [%wt.]
Hunicz et al. (2020) [3] diesel fuel 86.5 13.5 0 0.0006 0
Biodiesel elemental composition [%wt.]
Lotero et al. (2006) [164] biodiesel (FAME) 77.00 12.00 0 0.05 11.00

creased from 34.7% at 300°C to 75.6% at 600°C. Further elevating
the pyrolysis temperature to 700°C reduced aromatic content to
57.4%. The inverse trend was noticed for aliphatic compounds [59].
The authors, conducting single-stage pyrolysis with an atmosphere
of product gas at 497°C and 614°C; and with nitrogen gas at 516°C
and 617°C, also noted an inverse correlation between aromatics
and aliphatic compounds. Conversion of aliphatic compounds to
aromatics resulted from the secondary atomisation reaction, with
the Dies-Alder mechanism and condensation occurring at higher
temperatures [102,119,160].
De Marco Rodríguez et al. [86] stated that the correlation be-
tween aromatics and aliphatics is related to the recombination re-
action among free radicals of these compounds. Choi et al. [59,112]
observed that the dominant compounds of aromatic fraction, in-
dependent of the pyrolysis parameters, were xylenes, while DL-
limonene was the main aliphatic compound. Notably, these obser-
vations were irrespective of the process conditions, reactor type or
fluidised-bed material.
Among other aromatics, PAHs pose a challenge because they
are not only highly toxic as an exhaust gas compound but also
enhance soot formation. Aromatisation of aliphatic compounds to
PAHs is supported by high temperatures and residence time. Cun-
liffe and Williams [161], using a fixed-bed reactor, observed an in-
crease of the PAH content from 1.5%wt. to 3.4%wt. when shifting
temperature from 450°C to 600°C. Alvarez et al. [58], using a con-
ical spouted-bed reactor, produced PAH fractions lower than 5%wt
at temperatures of 475°C and lower. Elevating the temperature to
575°C increased the polyaromatic content to 12.6%wt. However,
some studies reported higher PAH concentrations, even in lower
temperatures. For example Li et al. [162] produced 8.6%wt. PAHs at
450°C and 13.1%wt. at 500°C in a rotary-kiln reactor. Interestingly,
further temperature rise did not increase PAHs production.
Table 5 summarises the elemental composition of different TPO
samples reported by individual authors and compares it the com-
position of DF and the most popular biodiesel (FAME). The pyroly-
sis process temperature is also given.
Analysis of Table 5’s summary of the TPO compositions shows
two tendencies are emerging. Luo and Feng [115] found that pyrol-
ysis temperature significantly affected the profile of individual el-
ements: raising the temperature significantly increased the shares
of C and N, while the H share gradually decreased. In contrast, de
Marco Rodríguez et al. [86], Galvagno et al. [121] and Aylón et al.
[98] did not observe significant changes in the elemental composi-
tion of TPO with temperature.
The quality of crude pyrolytic oil obtained from waste tyres
makes it generally suitable for use as fuel in a CI engine. TPO’s
heating value of approximately 43 MJ/kg is close to those of other
engine fuels, such as diesel (43.3 MJ/kg), methane (50 MJ/kg), gaso-
line (44.4 MJ/kg) and biodiesel (36.8 MJ/kg) [165,166]. It also has
similar molecular composition [86,103,115,163,164,167–171]. The
mass-based hydrogen to carbon ratio (affecting tank-to-wheel CO2
emissions) for crude TPO averages 0.128, similar to that of refined
diesel oil.
TPO’s properties relevant to its use in a combustion engine are
discussed in detail in the following section. One should bear in
mind that TPO’s composition, and hence its related combustion pa-
rameters, depends on reactor type, inert gas used, process temper-
ature, quality of feedstock and their pre-treatment. Subsequent re-

16
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
fining used as a post-treatment will also have a bearing on TPOś
combustion parameters.
3. Pyrolytic oil as engine fuel
Already in the early 1980s, it was found that pyrolytic oil sam-
ples and condensates produced by petroleum residues coking (by
thermal and steam cracking of gasoil fraction and gasoline) are
similar to olefins [103]. For this reason, these products can be
blended and thermally treated under the same conditions. Fur-
thermore, Miandad et al. [73] suggested that TPO generated by
catalytic and non-catalytic pyrolysis consisted mainly of aromatics
with some aliphatic compounds, which have similar physical prop-
erties as conventional diesel fuel.
As discussed in the introduction, this review focuses on CI
engine applications because these are the most feasible from the
future demand perspective. TPO samples should be evaluated
against legal and functional requirements in order to verify if TPO
is suitable as fuel for CI engines. Important properties, among oth-
ers, are kinematic viscosity, density, acidity, water content, sulphur
content, flash point, distillation curve and cetane number. The
following chapters review TPO’s engine-relevant properties and
possible quality improvement measures. Table 6 summarises the
results of the assessment of TPO as a CI-engine fuel. Automotive
diesel EN 590 standard is used as a reference in this table and in
the discussion.
3.1. Properties of crude TPO
Heating value (or calorific value) is one of the most important
indicators for fuel as it translates to the vehicle/vessel range and
is a key factor in the well-to-wheel CO2 assessment and the fuel
cost of transport. It should be noted here that mass-based heat-
ing value of hydrocarbon fuels is straightforwardly shaped by the
ratio of hydrogen to carbon and the presence of oxygen and nitro-
gen. In the case of biofuels and also TPO, water content can signif-
icantly harm calorific value. Heating values for the TPO samples in
Table 6 are depicted in one of three forms: higher and lower heat-
ing value (HHV and LHV respectively) or as gross calorific value
(GCV). This is because the individual study authors did not all
adopt the same measurement principle. The difference between
the three approaches relates to how water and ash content is han-
dled in the calculation. For further elaboration of this, refer, for in-
stance, to Heywood [188].
The energy density of crude TPO can be optimised to give
diesel-like values, with LHV ranging from 38.9 to 42.5 MJ/kg
[115,179,180]. Reported values of GCV usually range from 41.6 to
44.8 MJ/kg [88,90,103,174,175,177,183]. Some studies, with calorific
values ranging from 39.2 to 48.7 MJ/kg, fail to specify the method
used for its determination [72,106,111,178,184,187]. This spread of
values stems from differences in feedstock quality and different py-
rolysis process parameters. Studying Table 6 reveals that there is
no straightforward correlation between heating value and process
temperature. For instance, Luo and Feng [115] observed that both
parameters increase simultaneously, while Ramirez-Canon et al.
[111] observed a significant drop in HHV after elevating the process
temperature above 600°C. More detailed analysis, however, reveals
the direct correlation of heating value with TPO yield. Importantly,
there is no trade-off here: maximising yield also results in a higher
energy density of the end fuel. As with the case of mass fraction
yield, catalytic pyrolysis tends to produce more energetic fuel [72].
Note that, according to Ramirez-Canon et al. [111], the increase of
mass fraction yield translates to higher heating value by virtue of
increased density of the TPO sample. The increased density was
observed and ranged from 830 to 987 kg/m3 at 15°C, the latter
value significantly beyond that of EN 590 diesel.
17
Progress in Energy and Combustion Science 85 (2021) 100915
Most of the kinematic viscosity values for TPO (measured
at 40°C) were in accordance with EN 590ś permissible range
for diesel fuels, 2.0-4.5 mm2 /s [17,71,72,88,106,115,173,176,178–
182,184]. However, Ramirez-Canon et al. [111] and Miandad et al.
[73] both reported low viscosities - below 1.90 mm2 /s. On the
other hand, Islam et al. [175], Sebola et al. [177], Islam and
Nahian [183], Bhatt and Prajapati [186], Hürdoğan et al. [187] and
Ambrosewicz-Walacik et al. [39] obtained highly viscous TPO,
well above the level for proper operation of most fuel injection
systems. Roy et al. [103] for instance, recorded kinematic viscosity
(at 50°C) of 23.5 mm2 /s for his TPO obtained from passenger
car tyres filled with silica (fixed-bed reactor). It should be noted
that viscosity depends heavily on temperature, with hyperbolic
characteristics differing from fuel to fuel. For the discussed sample
the viscosity at 100°C was 5.2 mm2 /s. Its potential direct engine
application, for marine use, for instance, would require preheating
to around 120°C.
Water and sulphur concentrations in crude TPO are usu-
ally above the levels specified as maxima for EN 590 diesel
(water, 200 mg/kg; sulphur, 10 mg/kg). According to the avail-
able data, water contents varied between zero and 46 g/kg
[93,115]. Turning to sulphur content, all the samples presented
in Table 6 significantly exceeded the sulphur limit for EN 590
diesel. Values ranged from 88 mg/kg to 15 g/kg [17,39,71–
73,93,103,111,173,174,176,177,179,180,182,186]. Desulphurisation
methods are discussed in Section 3.3.
The flash point is the lowest temperature at which a liq-
uid can form an ignitable mixture with air, when the surface of
the liquid is exposed to an ignition source. It is related to the
volatility of the fuel, and is therefore set by distillation param-
eters. The EN 590 standard regulates the flash point of diesel
to be at least 55°C, enabling safe storage and handling. How-
ever, most research determines TPO’s flash point to be less than
30°C [71,73,88,103,175,180–182]. Some put it higher, from 31°C
to 54°C [17,39,72,111,173,174,183–186]. Only a few studies as-
sessed TPO’s flash point to be in accordance with the require-
ments of the EN 590 standard, reporting values from 58°C to 94°C
[103,106,159,177–179].
One of the most important fuel characteristics is the distillation
curve, which can explain the trends in several parameters already
discussed: flash point, volatility and low-temperature properties.
Fig. 11 shows distillation curves of TPO produced at different reac-
tor temperatures, determined by Alvarez et al. [58]. For reference,
gasoline, diesel and vacuum gas oil distillation curves are included
in Fig. 11. Note, however, that the distillation curve of TPO is sim-
ulated – based on the detailed chemical analysis. Fig. 12 shows ex-
perimental distillation curves determined by de Marco Rodríguez
et al. [86] and Yazdani et al. [11].
The distillation range of TPOs in Fig. 11 shows that pyrolytic
oils consist of a wide variety of chemical products with different
boiling points. The exception to this is case 6, which was pyrol-
ysed at the highest temperature (575°C) and which shows a rela-
tively flat distribution, consisting mostly of fractions with a boiling
point around 160°C. The other curves show that the gasoline frac-
tion of TPO, also called light naphtha fraction, with boiling temper-
atures < 160°C, varies from 14% to 42%. The heavy naphtha fraction
(160-200°C) reported by Yazdani et al. [11] for pyrolysis tempera-
ture 500°C was only 4%, whereas from Fig. 11 it can be read that
at the process temperature 575°C this fraction constitutes approx-
imately 70% of the TPO. The middle distillate fraction (from 200°C
to 350°C) is reported to be between 35% and 38%, and the heavy
oil fraction (> 350°C) ranges from 1% to 47% [11,58,86]. Generally,
a wider distillation temperature range than for DF inhibits the low-
temperature properties of TPO, at the same time causing issues
related to low flash-point. The low-temperature issues come from
large fractions of heavy components. While typically 95% of diesel
 Table 6
Physicochemical characteristics of TPO and DTPO

Reference Additional information Temperature Crude or Calorific Density Kinematic Water Sulphur Flash Cetane
of pyrolysis distilled value @15°C viscosity content content point number
[°C] [MJ/kg] [kg/m3 ] @40°C [%wt.] [%wt.] [°C] [-]
[mm2 /s]

EN 590 [172] - - - 42-44 (LHV) 820-845 2-4.5 0.02 0.001

M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.

≥ 55 ≥ 51
TPO, DTPO or fraction of TPO (light, medium and heavy)

Roy et al. (1999) [103] passenger car tyres 520 Crude 43.6 (GCV) 950 (20°C) 9.7 (@50°C), 0.3 0.8 28 44
3.2 (@100°C)
passenger car tyres filled with silica 500 Crude 43.8 (GCV) 976 (20°C) 23.5 (@50°C), 1.6 1.5 59 n.a.
5.2 (@100°C)
fixed-bed reactor, truck tyres 485 Crude 44.8 (GCV) 939 (20°C) 17.8 (@50°C), 1.5 1.0 22
6.0 (@100°C)
Ucar et al. (2005) [88] fixed-bed reactor, passenger car tyre 650 Crude 41.6 (GCV) 943 4.62 n.a. n.a. <30
truck tyre 650 Crude 42.4 (GCV) 913 3.85 <30
Murugan et al. (2008) [173] steel pyrolysis reactor, atmosphere 450-650 Crude 38.0 (net 934 3.77 0.72 43
vacuum calorific
value)

18
Murugan et al. (2008) [174] steel pyrolysis reactor, 450-650 Crude 42.8 (GCV) 935 3.20 0.95 43
Distilled 45.6 (GCV) 871 1.70 0.03 36
Islam et al. (2008) [90] fixed-bed reactor 575 Crude 42.0 (GCV) 957 4.75 (@30°C) n.a. ≤ 32
Islam et al. (2010) [175] fixed-bed reactor 475 Crude 41.6 (GCV) 943 4.62 ≤ 30
İlkılıç and Aydın (2011) [176] pyrolysis reactor was electrically 700 Crude n.a. 945 (20°C) 3.85 0.90 50 44
heated
Sebola et al. (2013) [177] n.a. n.o. Crude 43.0 (GCV) 926 (20°C) 9.0 3.54 0.91 94 n.a.
Distilled 43.7 (GCV) 807 (20°C) 1.50 0.065 0.41 44
Wongkhorsub and [178] batch pyrolysis reactor 350-400 Distilled 43.2 n.a. 2.69 n.a. n.a. 68
Chindaprasert (2013)
Frigo et al. (2014) [179] thermo-mechanic cracking reactor 500 Crude 41.96 (LHV) 903 2.90 0.033 0.97 58
Martínez et al. (2014) [180] continuous auger reactor 550 Crude 40.5 (LHV) 917 2.39 0.068 0.83 23
Tudu et al. (2014) [181] rotary type reactor 375-440 Light fraction 39.2 910 3.06 n.a. 1.17-3.00 30 25-30
Al-Lal et al. (2015) [182] n.a. no data Crude 40.5 (LHV) 917 2.40 0.069 0.83 23 n.a.
Vihar et al. (2015) [105] vacuum pyrolysis 600-700 Crude 40.6 (LHV) n.a. 3.22 (@20°C) 0.012 n.a. n.a.
Ayanoğlu and Yumrutaş (2016) [71] n.a. 450 Crude 41.0 (HHV) 830 3.21 n.a. 0.013 28.1
Al Mamum et al. (2016) [93] fixed-bed reactor 320-390 Distilled - 840 0.668 nil 0.629 8
Islam and Nahian (2016) [183] cylindrical chamber as a reactor 450-600 Crude 42.0 (GCV) 956 16.39 n.a. n.a. 50
450-600 Distilled 43.6 (GCV) 835 0.89 < 10
(continued on next page)
Progress in Energy and Combustion Science 85 (2021) 100915
 Table 6 (continued)
Wang et al. (2016) [184] lab-scale fixed-bed reactor, N2 350 Crude 42.1 887.2 2.71 n.a. n.a. 39 44
atmosphere 400 42.1 889.1 2.74 40 43
450 42.2 890.4 2.81 43 45
Ambrosewicz-Walacik and [185] n.o. 450-500 Crude n.a. 955 5.68 0.49 53 n.a.
Walacik (2017)
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.

Bhatt and Prajapati (2017) [186] rotary reactor 430 Crude 910 8.65 Nil 0.0088 32 42
Hürdoğan et al. (2017) [187] axis rotary type reactor 500-550 Crude 40.1 907 4.98 n.a. n.a. > 100 n.a.
Luo and Feng (2017) [115] sole pyrolysis 1000 Crude 38.5 (HHV) 982.7 3.91 1.56 n.a.
pyrolysis with ceramin balls 1000 Crude 40.2 (HHV) 944.8 3.62 2.07
catalytic pyrolysis with BF slags 1000 Crude 44.1 (HHV) 935.2 2.10 4.57
pyrolysis using BF slag 600 Crude 38.9 (LHV) 941.2 3.69 1.56
700 Crude 40.6 (LHV) 961.9 3.06 2.68
800 Crude 41.0 (LHV) 986.9 3.29 3.97
900 Crude 41.6 (LHV) 955.0 2.35 4.11
1000 Crude 42.1 (LHV) 982.7 2.10 4.57
Sharma and Murugan (2017) [17] n.a. n.a. Crude 38.1 n.a. 3.35 n.a. 0.95 49 28
Ambrosewicz-Walacik et al. [39] 450-500 Crude n.a. 955.0 5.68 0.49 53 n.a.

19
(2018) pyrolytic oil distilled at three Light 770.0 0.823 0.40 < 3.5
different temperatures Medium 1003.0 0.842 0.60 12.0
Heavy 1360.0 0.891 0.85 25.0
Banihani and Bani Hani (2018) [72] pyrolysis without catalyst 550 Crude 43.5 911.7 4.60 1.13 50 45
(@20°C)
pyrolysis with alumina catalyst 551 Crude 45.5 862.8 3.90 0.37 55 45
(@20°C)
pyrolysis with zeolite catalyst 552 Crude 48.3 858.6 3.60 0.34 56 48
(@20°C)
Miandad et al. (2018) [73] pyrolysis with activated alumina 600 Crude 42.5 (HHV) 900 1.90 n.a. 27 n.a.
Ramirez-Canon et al. (2018) [111] pyrolysis with hydrogen steam 450 Crude 48.7 830 1.59 0.90 1.09 32.0
500 47.2 850 1.88 0.75 1.06 32.5
550 47.4 880 2.77 0.75 0.89 30.5
600 46.9 860 2.65 0.35 1.07 35.5
450 with H2 45.9 860 2.35 0.55 0.87 34.5
500 with H2 48.1 850 2.41 0.40 0.78 30.5
550 with H2 47.3 870 2.48 0.25 0.67 31.0
600 with H2 47.9 880 3.07 0.30 0.80 31.0
Progress in Energy and Combustion Science 85 (2021) 100915
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 11. Simulated distillation curves of TPOs obtained at 442°C, 475°C and 575°C
with reference curves of commercial fuels and vacuum gas oil. Reproduced from
[58] with permission from Energy, Elsevier.
Fig. 12. Distillation curves of TPOs obtained at 500°C by de Marco Rodríguez et al.
[86] and at 550°C by Yazdani et al. [11]. Reproduced from [11] with permission from
Waste Management, Elsevier.
fuel distillates below 340°C, this characteristic temperature for TPO
can be as high as 500°C. The low flash point (flammability) issue
relates to some fraction of gasoline-like components with low boil-
ing temperatures.
The distillation curves of crude TPO suggest that both the flash
point and low-temperature properties could be improved if nar-
rower fractions are isolated by further distillation. The properties
of distilled TPO are presented in the next subsection.
Cetane number (CN) is of great importance because it deter-
mines the fuel’s ability to auto-ignite under CI engine conditions.
The EN 590 standard for automotive-grade fuels specifies a min-
imum cetane number of 51, whereas values for crude TPO are
rather lower, ranging from 25 to 48 [17,72,103,106,176,184,186].
20
Progress in Energy and Combustion Science 85 (2021) 100915
Such values indicate that compression ignition in typical engine
conditions is still possible, but with significant ignition delay. How-
ever, lower CN does not preclude TPO use in other engine applica-
tions, such as off-road or marine (see Table 1 for reference). One
should note that the cetane number is shaped by chemical compo-
sition of hydrocarbons. Generally, normal paraffinic hydrocarbons
exhibit the best auto-ignition properties, whereas branched paraf-
fins, olefins and aromatics reduce the cetane number. Additionally,
a greater number of C atoms leads to better auto-ignition proper-
ties, but carries the penalty of higher viscosity [188,189].
Another obstacle to TPOś application is its acidity, which af-
fects corrosive activity and propensity to create deposits. Acidity
usually does not pose a challenge for mineral DF, while for biofu-
els it is an issue, mainly due to some content of carboxylic acids.
Both European and US standards (EN 14214 and ASTM D6751) limit
acid value of biofuels to 0.5 mg KOH/g. TPO also contains some
amounts of carboxylic acids and additionally can contain sulphuric
acids. However, different research provides very different acidity
levels. Ambrosewicz-Walacik et al. [39] determined acidity to be
4.33 mg KOH/g. Antoniou and Zorpas [190] reported a much lower
value of 0.45 mg KOH/g. Raj et al. [81] demonstrated diesel-like
acidity (0.1-0.21 mg KOH/g). Alvarez et al. [58] and Yazdani et al.
[11], independently indicated that the content of carboxylic acids
in TPO drops with increasing pyrolysis temperature. However, com-
parison of other studies’ acid values and process temperatures do
not support this statement. These discrepancies suggest that acid-
ity of TPO is affected by many factors, not yet sufficiently studied
in the literature.
Finally, long-term storage capabilities are an important con-
sideration for new fuels or their components. Storage capabili-
ties of fuels are affected mainly by oxidation, thermal or thermal-
oxidative decomposition, hydrolysis or microbial contamination
from dust or water [JH003]. Oxidative stability is one of the pri-
mary concerns, but high water-content in TPO might also involve
issues of hydrolysis and microbial growth. Nevertheless, available
reports mention satisfactory storage capabilities of TPO. Alvarez
et al. [58] stated that TPO properties remain unchanged with time.
More quantitatively, Ambrosewicz-Walacik et al. [185] determined
oxidative stability of the TPO distillate (EN 14112 method), to be
above 20 hours – a value considered sufficient for EN 590. Sharma
and Murugan [17] pointed out that TPO contains some phenolic
compounds, which may act as antioxidants. They observed that
20% TPO admixture in biofuel – jatropha methyl ester (JME) - im-
proved oxidation stability approximately 2.5 times. Moreover, the
stability effect of TPO admixture was greater than that of DF. Ac-
cording to the above remarks, TPO seems to support oxidative sta-
bility of biofuels when blends are considered.
3.2. Properties of TPO distillates (DTPO)
Distillation is one of the main methods to improve TPO fuel
quality, with different fractions being more suitable for different
applications, either as fuel or as a fuel additive. The distillation
curves of TPOs (see previous subsection for reference) show that
pyrolytic oils consist of wide variety of chemical products with dif-
ferent boiling points. Literature specifying the properties of differ-
ent TPO fractions is, however, limited. Where available, properties
of TPO distillates are included in Table 6, providing comparison
with the properties of crude TPO obtained via the same pyrolysis
process.
The recent work by Ambrosewicz-Walacik et al. [39] outlines
the systematic fractionation of TPO, along with an assessment of
the physicochemical properties of the fractions obtained. Three lev-
els of distillation were considered: A) Light Fraction: consisting of
components with boiling temperature < 160°C. This fraction was
distilled in order to separate components with high volatility, sig-
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 13. Crude TPO sample (left) and products of its distillation analysed in
Ambrosewicz-Walacik et al. [39]; A – light naphtha fraction, B – medium fraction,
C – heavy fraction; author’s archive.
nificantly influencing the low flash point of the pyrolytic oil. B)
Medium Fraction: boiling temperature from 160°C to 204°C. This
fraction was considered as a diesel fuel component and subjected
to further engine tests in [39]. C) Heavy Fraction: components with
boiling temperature from 205°C to 350°C. Note that at over 350°C,
only a tar-like substance remained in the distillation flask. As well
as the physicochemical comparison given in Table 6, the differ-
ences in the appearance of crude TPO and its distillates are seen
in Fig. 13. It clearly shows that the added value of distillation is
the reduction of ash and tar content in the fuel [39].
It was shown that the distillation process dramatically reduced
kinematic viscosity (to below 0.9 mm2 /s for all samples) while
also contributing to the unfavourable decrease of the flash point
(Table 6). The flash point for the light fraction was below 3.5°C;
it was 12°C and 25°C for the medium and heavy fractions respec-
tively. The crude TPO’s flash point was 53°C, almost meeting EN
590’s threshold value of 55°C for diesel.
Other authors had studied only selected distillates, usually
medium and light fractions, but the above trends were confirmed
by Al Mamun et al. [93], Islam and Nahian [183] and Murugan
et al. [174]. Describing what they called a light TPO fraction, Tudu
et al. [181] reported viscosity of 3.06 mm2 /s (within EN 590’s per-
mitted range) and a moderate flash point of 30°C.
Murugan et al. [174], Sebola et al. [177] and Islam and Nahian
[183] recorded that the distillation process contributed to the in-
crease in calorific value of analysed samples. Their medium frac-
tions had respectively 2.8 MJ/kg, 0.7 MJ/kg and 1.6MJ/k higher en-
ergy density than their individual crude TPO samples. At the same
time, it is difficult to assess how distillation affects CN. Actually,
only Tudu et al. [181] reported that their fractionated light DTPO
product had a CN of 25-30 (depending on the pyrolysis tempera-
ture) while having a more or less constant calorific value of 39.2
MJ/kg. However, that work lacks any comparison with the crude
TPO. Its authors also reported the light fraction’s very high sen-
sitivity to sulphur penetration, depending upon pyrolysis process
temperature. Its sulphur content varied from 1.2% to above 3%wt.
From Ambrosewicz-Walacik et al. [185] we can deduce that the
sulphur content of fractions follows the same trend as density.
The light fractions accumulated less sulphur than the baseline TPO
(0.40%wt. vs 0.49%wt.), while having significantly lower density
than crude TPO (770 kg/m3 vs 955 kg/m3 ). The medium fraction
already had both indicators slightly above baseline TPO. The heavi-
est fraction had a density of 1360 kg/m3 and sulphur concentration
of 0.85%wt.
3.3. Quality improvement measures for TPO/DTPO
Section 3.1’s and 3.2’s review of TPO/DTPO parameters related
to use as fuel in a CI engine reveals a large spread in the results
obtained in different reactors. Nevertheless, it is clear that most of
TPO’s physicochemical parameters did not meet the EN 590 stan-
dard. In the case of a few determinants, depending on pyrolysis
methods, nor did TPO comply with other standards. For example,
21
Progress in Energy and Combustion Science 85 (2021) 100915
it did not meet ISO 8217 for bunker fuel quality. Sulphur content
and moisture levels of the TPO fuel present the biggest issues. At
this point, it is necessary to mention that, in principle, TPO can
be used as feedstock to standard refinery processes to produce
automotive-grade diesel and other fuels. However, this route has
not been demonstrated openly and consequently will not be cov-
ered in this review.
Moisture removal does not pose a particular challenge and can
be achieved with a variety of well-established methods which
are standard for many alternative fuel components. These meth-
ods involve mechanical separation (centrifugation), physical pro-
cesses (percolation through a bed of anhydrous substance such as
sodium sulphate, vacuum drying) or thermal processing (distilla-
tion) [47,174,181]. There are also chemical methods based on sup-
plementation with additives exhibiting water-binding properties
[191]. As mentioned, these methods are commonplace and thus
will not be separately discussed. Moisture removal helps increase
the heating value and improve the CN of the fuel and is important
from the perspective of preventing engine corrosion and tribologi-
cal issues [106].
Sulphur content of liquid engine fuels has been drastically re-
duced in the past few decades, cutting the sulphur compounds
in exhaust emissions. These are environmentally harmful, mainly
because of their potential to cause acid rain. Furthermore, fuel
sulphur increases particulate matter and soot emissions in inter-
nal combustion engines [192]. There are also technical reasons for
cutting fuel sulphur: sulphur causes corrosion and has a delete-
rious effect on advanced catalytic systems used for CO, HC, NOx
and particulate reduction [193,194]. This underlines the impor-
tance of desulphurisation for TPO, especially bearing in mind the
possible direct use of TPO in shipping, where IMO has introduced
0.5/0.1%wt. fuel sulphur limits. The automotive EN 590 standard
is already very stringent, limiting fuel sulphur content to just 10
mg/kg (0.001%wt.).
The sulphur in pyrolytic oil is related to the fact that this
compound is used as a cross-linking agent during tyre manufac-
turing. Sulphur-containing compounds undergo different reactions
(recombination and/or disproportionation) during pyrolysis. As dis-
cussed in Sections 3.1 and 3.2, TPO/DTPO may contain different
amounts of sulphur, depending on the process conditions and dis-
tillation temperature.
A conventional refinery hydrodesulphurisation (HDS) process
can be used to reduce sulphur content in fuel, yet its appli-
cation is primarily limited to distillates (light to medium frac-
tions) [195]. Debek
˛ and Walendziewski [74] applied hydrotreat-
ment with a NiMo–Al2 O3 catalyst (a standard refinery configura-
tion for petroleum-based products), cutting sulphur content from
1.1% to 0.2%. Additionally, double carbon bonds were effectively de-
stroyed. This required quite strict hydro-refining conditions, using
360°C and 5 MPa H2 pressure. Hita et al. [196,197] also performed
HDS with a NiMo catalyst, while trying six different porous sup-
ports, including a conventional composition with -Al2 O3 , as in the
previously referred study. The authors selected –Al2 O3 , SiO2 –Al2 O3
and a mesoporous material referred to as MCM-41 as the most ac-
tive catalytic supports. All of them provided roughly equal sulphur
removal potential of around 90% for TPO samples with 2% and 1%
sulphur content, leaving 0.2% and 0.1% sulphur respectively in the
end samples. The differences were observed in H2 uptake and fi-
nal fuel composition. The SiO2 –Al2 O3 -based catalyst provided the
highest yield of diesel (57%wt.) and naphtha (25%wt.), while the
conventional –Al2 O3 setup gave the highest fuel quality, charac-
terised by an increased paraffinic fraction and improved CN. The
latter was as much as five points higher than the base TPO.
The above numbers indicate that state-of-the-art HDS has po-
tential to reduce the sulphur content of crude TPO to the level
of 0.1%, independently of the base sampleś sulphur content. It
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
should be noted that high consumption of hydrogen, expensive
molybdenum catalysts and low stability of the support materi-
als deemed effective for TPO HDS are considered as disadvantages
of this method [195,197]. Refining processes that remove sulphur
from the fuel also simultaneously reduce the fuel’s lubricity.
Another popular desulphurisation method uses oxidation of the
sulphur compounds, either by methanol extraction or silica gel col-
umn adsorption of the more polar, oxidized sulphur compounds
from methanol. Al-Lal et al. [182] used both methods on TPO pro-
vided by a third party, yet failed to lower the sulphur content to a
significant degree.
There were a couple of successful attempts to reduce TPO’s
sulphur by optimising the pyrolysis process itself, either by ded-
icated reactor conditioning or by adding catalysts. Analysis of
Table 4 shows that the application of catalysts during pyrolysis
could be effective in lowering TPO’s sulphur content. Banihani and
Bani Hani [72] employed this technique to cut sulphur in pyrolytic
oil by around 70%. The sulphur content of 1.13% in their TPO with
baseline tyre pyrolysis without a catalyst was cut to 0.37% and
0.34% when alumina and zeolite catalysts respectively were added
to the process. Importantly, in both catalytic cases, the reduction in
sulphur was accompanied by improvement of all the other proper-
ties of the TPO (refer to Table 6 for details).
Note that already in 20 0 0 Murena [198] considered using hy-
drogenative pyrolysis to reduce TPO’s sulphur content. Coupled
with optimising the feedstock pre-treatment (tyre scrap versus tyre
powder), the author observed that the use of tetralin as a hydro-
gen donor could cut sulphur by 30%. However, the tyre/tetralin ra-
tio used to achieve this degree of sulphur reduction was over 1:3,
so the large amount of hydrogen donor solvent required could sig-
nificantly influence the economics of tyre pyrolysis rendering this
method uncompetitive.
Choi et al. [59,112] tackled sulphur reduction by using differ-
ent reactor conditions and reactor addification. They concluded
that, independent of the pyrolysis process (single-stage or two-
stage) and type of inert gas (product gases or N2 ), raising py-
rolysis temperature generally increases the sulphur content, with
different sensitivities for individual pyrolysis types [59]. Using N2
as the fluidising medium with two-stage pyrolysis generally facil-
itated the lowest sulphur in crude TPO. Sulphur accumulation de-
creased from 0.92%wt. at baseline conditions (single-stage; prod-
uct gases; temperature optimised for liquid yield), to 0.55% at op-
timised operation (sulphur content co-optimised with temperature
for maximum TPO yield and heating value). In the follow-up work,
Choi et al. started from the previously optimised pyrolytic reactor
and experimented with different process additives (dolomite and
olivine, both natural and calcined) in search of a further reduction
in the TPO’s sulphur [112]. The TPO sample produced with natu-
ral and calcined olivine contained low amounts of sulphur (0.46
and 0.45%wt. respectively). Interestingly, the addition of natural
dolomite increased sulphur to 0.70%wt., while calcine dolomite had
no significant effect.
Aydın and İlkılıç [118] investigated the effect of adding CaO
and Ca(OH)2 as sulphur-mitigating agents to a pyrolytic reactor fed
with tyre scraps. After optimising the amount and ratio of both
compounds the authors demonstrated a reduction in sulphur con-
tent from 1.4%wt. to 0.9%wt., without significantly impacting other
TPO parameters. Additional post-pyrolysis desulphurisation with
sulphuric acid (10% aqueous solution) cut the sulphur content to
0.2% wt.
This latter post-treatment method is commonly referred to as
desulphurisation through ionic solutions or liquid-liquid extraction.
Ahmad et al. [199] analysed the impact of various desulphurising
ionic agents on TPO, using sulphuric acid; a combination of hydro-
gen peroxide and acetic acid; Fuller’s earth; and calcium oxide. A
15%wt. solution of sulphuric acid as the extracting medium gave
22
Progress in Energy and Combustion Science 85 (2021) 100915
the maximum sulphur reduction, cutting the TPO’s sulphur con-
tent from the baseline approximately 1%wt. to 0.63%wt. Interest-
ingly, calcium oxide showed only a marginal desulfurisation abil-
ity although the cited authors did refer to the already mentioned
successful result by Aydın and İlkılıç [118]. Ahmad et al. supposed
that using calcium oxide at higher temperatures would give a big-
ger sulphur reduction [199]. They also found that the viscosity of
tyre pyrolysis oil fell significantly with increasing addition of sul-
phuric acid and the hydrogen peroxide/acetic acid combination.
Viscosity was not similarly affected by the addition of calcium ox-
ide, however. Also evaluating ionic solutions, Koc and Abdullah
[200] started desulphurisation by preparing a binary solution of
tetraoctylammonium bromide and hydrogen peroxide (30% purity),
to which a phosphotungstic acid catalyst was added. The presented
solution cut the sulphur content in the TPO sample from 0.768%wt.
to 0.321%wt.
In summary, recent years have brought significant progress in
new desulphurisation techniques for TPO. Despite this progress,
none of the reviewed works actually managed to demonstrate
compliance with EN 590’s stringent sulphur limit of just 10 mg/kg
(0.001%wt.) for automotive diesel. However, the IMO ECA sulphur
limit of 0.1%wt. is apparently already within range for TPO and fur-
ther sulphur reduction can be achieved by combining the individ-
ual measures discussed in this section [186].
3.4. Blending with other fuels and TPO addification
The previous sections´discussions on TPO’s physicochemical
properties such as density, viscosity, sulphur content, flash point
and CN, clearly lead to the conclusion that it is not feasible to
use pure TPO as an automotive drop-in fuel. However, blending
TPO or DTPO with DF, biodiesel or SVO is possible, while keeping
blended fuel properties within standards. Moreover, some specific
properties of the TPO/DTPO can be utilised for regulation of the
overall properties of the fuel. This section reviews the state of re-
search into TPO/DTPO blends with other fuels and is summarised
in Table 7.
Currently, there appears to be little attention paid to research
into use of crude TPO in binary mixtures with mineral diesel. Hür-
dogan et al. [187] analysed blends consisting of 50, 80 and 90%vol.
of crude TPO and corresponding amounts of DF. The authors ob-
served a gradual reduction of the mixture’s density and kinematic
viscosity as the proportion of DF was increased. Values of den-
sity and kinematic viscosity for TPO50 (50% TPO) were significantly
lower than for neat TPO and were in accordance with the require-
ments of EN 590. Note that the flash point of their baseline TPO
was surprisingly high (> 100°C), so the authors did not consider
this as a constraint. CN, however, was not reported.
Martínez et al. [180] investigated a blend of 5%vol. crude TPO
and 95%vol. of DF. They achieved a fuel compatible with the au-
tomotive diesel standard in all aspects except water and sulphur
content: their values exceeded EN 590 limits by 100%. This was
due to a rather high content of both species in the crude TPO.
Sharma and Murugan [201] used biodiesel produced from jat-
ropha oil to prepare blends using the addition of crude pyrolytic
oil, from 10% to 50%. The cited authors found that increasing the
share of jatropha methyl esters reduced the blend’s density, while
kinematic viscosity and flash point increased. Additionally, the an-
tioxidative properties of TPO were utilised to compensate for weak
biofuel oxidative stability. A similar tendency was observed in the
later work of the same authors [17]. The authors claimed that
biodiesel and TPO are complementary in terms of viscosity (too
high for biodiesel), flashpoint (too high for TPO) and CN (too low
for biodiesel). The 20% admixture of TPO was considered the near-
est to meeting EN 590: only its sulphur content and viscosity were
slightly too high. This could have been corrected by more efficient
 Table 7
Basic characteristics of monocomponent, binary and ternary mixtures of TPO/DTPO
Composition of mixtures [%vol.] Calorific Density @15°C Kinematic Water content Sulphur content Flash point Cetane
Reference value [kg/m3] viscosity [%wt.] [%wt.] [°C] number
Rapeseed oil
[MJ/kg] @40°C [-]
TPO DTPO DF Biodiesel (SVO) Others
[mm2 /s]
Monocomponent mixtures (TPO/DTPO)
Murugan et al. [174] 100 - - - - - 42.80 935 3.2 n.a. 0.95 43.0 n.a.
(2008b) (GCV)
- 100 - - - - 45.60 871 1.7 0.03 36.0
(GCV)
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.

Murugan et al. [47] - 100 - - - - 43.7 807 (20°C) 1.5 0.065 0.41 44.0
(2008c) (GCV)
Sharma and Murugan [201] 100 - - - - - 39.2 920 (20°C) 5.4 n.a. n.a. 43.0
(2013)
Martínz et al. (2014) [180] 100 - - - - - 42.70 917 2.39 0.069 0.83 23.0
(HHV),
40.49
(LHV)
Al Mamun et al. [93] - 100 - - - - - 840 0.668 nil 0.629 8.0
(2016)
Tudu et al. (2016) [106] - 100 - - - - 39.20 910 3.06 n.a. n.a. 75.0 25-30
- - - - - 100 DMC 15.78 1.079 0.625 18.0 35-36
Ambrosewicz-Walacik [185] - 100 - - - - n.a. 870 1.05 1.22 12 n.a.
and Walacik (2017)
Hürdoğan et al. [187] 100 - - - - 40.13 907 4.98 n.a. >100
(2017)

23
Sharma and Murugan [17] 100 - - - - - 38.10 913 3.35 0.95 49.0 28
(2017)
Ambrosewicz-Walacik [39] - 100 - - - n.a. 955 5.68 0.49 53 n.a.
et al. (2018)
Binary mixtures
Murugan et al. [174] - 80 20 - - - 46.40 832 1.94 n.a. 0.23 47.0 n.a.
(2008b) (GCV)
- 90 10 - - - 45.80 865 1.73 0.23 37.0
(GCV)
Murugan et al. [47] - 80 20 - - - 45.90 860 1.76 0.21 39.0
(2008c) (GCV)
- 90 10 - - - 45.90 865 1.73 0.23 37.0
(GCV)
- 5 95 - - - 44.8 837 (20°C) 2.9 0.021 0.067 50.0
(GCV)
- 10 90 - - - 44.8 837 (20°C) 2.8 0.021 0.085 48.0
(GCV)
- 15 85 - - - 44.7 837 (20°C) 2.5 0.014 0.106 42.0
(GCV)
- 20 80 - - - 43.7 837 (20°C) 2.4 0.017 0.206 44.0
(GCV)
- 25 75 - - - 43.7 836 (20°C) 2.2 0.011 0.226 38.0
(GCV)
- 30 70 - - - 43.7 836 (20°C) 2.0 0.007 0.233 34.0
(GCV)

(continued on next page)

Progress in Energy and Combustion Science 85 (2021) 100915
 Table 7 (continued)
Reference Composition of mixtures [%vol.] Calorific Density @15°C Kinematic Water content Sulphur content Flash point Cetane
TPO DTPO DF Biodiesel Rapeseed oil Others value [kg/m3] viscosity [%wt.] [%wt.] [°C] number
(SVO) [MJ/kg] @40°C [-]
[mm2 /s]
Sharma and Murugan [201] 10 - - 90 (Jatropha) - - 39.24 883.5 (20°C) 5.73 n.a. n.a. 64.0
(2013) 20 - - 80 (Jatropha) - - 37.74 887.0 (20°C) 5.60 60.0
30 - - 70 (Jatropha) - - 36.40 892.3 (20°C) 5.41 55.0
40 - - 60 (Jatropha) - - 35.12 894.0 (20°C) 5.29 49.0
50 - - 50 (Jatropha) - - 33.89 897.5 (20°C) 5.15 44.0
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.

Martínez et al. (2014) [180] 5 - 95 - - - 45.02 (HHV), 848 2.73 0.008 0.04 n.a. n.a.
42.23 (LHV)
Al Mamun et al. [93] - 50 50 - - - - 833 1.44 nil 0.621 8.0
(2016)
Tudu et al. (2016) [106] - 40 60 - - - 41.96 862 2.87 n.a. n.a. 32.0 41.17
Hürdoğan et al. [187] 90 - 10 - - - 41.91 872 4.15 75.7 n.a.
(2017) 80 - 20 - - - 42.80 843 3.13 73.5
50 - 50 - - - 44.05 839 2.91 72.5
Sharma and Murugan [17] 20 - - 80 (jatropha) - - 38.82 887 5.20 0.18 132 52
(2017) 40 - - 60 (jatropha) - - 38.60 894 4.90 0.39 119 48
60 - - 40 (jatropha) - - 38.00 901 4.79 0.56 108 45
Jeyakumar et al. [203] 20 - 80 - - - 43.17 (NCV)∗∗ 831 2.93 n.a. 65 54
(2018)
Ternary mixtures
Tudu et al. (2016) [106] - 40 50 - - 10 39.15 779 2.78 n.a. n.a. 38.8 40.60
DMC∗

24
Ambrosewicz-Walacik [185] - 1.00 49.50 49.50 (frying - - n.a. 853 3.30 0.0061 37 n.a.
et al. (2017) oil)
- 0.91 35.78 63.31 (frying - - 848 3.38 0.0063 36
oil)
- 2.00 49.00 49.00 - - 849 2.93 0.0123 31
(frying oil)
- 1.98 38.62 59.40 - - 852 3.21 0.0122 29
(frying oil)
Ambrosewicz-Walacik [39] - 5 40 - 55 - 865 11.42 0.027 55
and Walacik (2018)
Jeyakumar et al. [203] 20 - 80 - - 43.10 (NCV) ∗∗
830 2.89 - 68 55
(2018) CaCO3
20 - 80 - - TiO2 43.08 829 2.87 - 67 55
Mikulski et al. (2019) [41] 5 40 - 55 - 39.5 (LHV) 868 11.56 0.0271 54.5 n.a.
5 45 - 50 - 39.6 (LHV) 861 8.94 0.0277 55.0
5 50 - 45 - 40.1 (LHV) 860 8.43 0.0275 56.0
5 55 - 40 - 40.7 (LHV) 852 7.97 0.0276 56.5
5 65 - 30 - 41.1 (LHV) 851 6.63 0.0140 57.0

∗
DMC - dimethyl carbonate
∗∗
NCV- net calorific valueThe distilled medium fraction of TPO obtained by Ambrosewicz-Walacik and Walacik [185] had extremely low viscosity. Hence, it was considered that only minor addition of this DTPO (between 1%vol.
and 2%vol.) would be sufficient for use as a viscosity improver. This was tested by adding it to a variety of blends comprising diesel and methyl esters produced from frying oil, all of which suffered from viscosity issues. The
thesis was verified negatively since the density and kinematic viscosity of the blends did not improve significantly after the addition of DTPO. However, even this small addition of pyrolytic oil contributed to a significant increase
in sulphur content and a reduction of flash point. The amount of sulphur was mostly determined by how much DTPO was added.
Progress in Energy and Combustion Science 85 (2021) 100915
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
desulphurisation of the baseline TPO and by use of a viscosity im-
prover. Flash point values of all tested mixtures complied with EN
590. However, it is worth noting that the claimed flash point val-
ues reported for corresponding blends in Sharma and Murugan
[17] and their earlier work [201] are significantly different (see
Table 7). Thus, the absolute values should be treated with caution
but the general statement regarding compliance of all the tested
mixtures with EN 590’s flash point limit still holds.
Other authors considered the use of distilled TPO to produce
binary mixtures with diesel or biodiesel. Murugan et al. [47,174]
examined DTPO blends with DF, using 80%vol. and 90%vol. DTPO
and 20%vol. and 10%vol. DF. They observed little changes in anal-
ysed properties such as density, kinematic viscosity, sulphur con-
tent and flash point compared with neat DTPO. Addition of DF ob-
viously improved all these properties but such high proportions of
DTPO (80% or more) with DF should be rather considered as an
academic idea because the resultant blend still falls well short of
EN 590. Al Mamun al. [93] investigated the parameters of a 50/50
blend of TPO and DF: their results led them to conclude even a
50/50 blend cannot satisfy EN 590. The authors, however, pointed
out that DTPO’s very low viscosity of 0.668 mm2 /s makes it suit-
able as a viscosity improver. Tudu et al. [106] added 40% DF to
their baseline DTPO and noticed the significant reduction in kine-
matic viscosity and density. The calorific value and cetane number
were close to the weighted (by volumetric shares) average of the
values of the individual components. As a cautionary note, the 40%
addition of DF reduced the flash point from the neat DTPO sam-
ple’s 75°C to just 32°C, implying that the fuel used as DF represen-
tative did not meet the EN 590 flash point requirement.
Tudu et al. also prepared a ternary blend, with 40%vol. of DTPO,
50%vol. of DF and 10%vol. of dimethyl carbonate (DMC) [106]. This
had significantly lower density and slightly lower kinematic vis-
cosity than the binary blend, but suffered from reduced calorific
value and cetane number index. Hariharan et al. [202] also sug-
gested that diethyl ether could be used as a cetane number im-
prover for TPO. The second part of Table 5 and the following dis-
cussion review ternary mixtures using TPO/DTPO as a component.
Follow-up works by Ambrosewicz-Walacik et al. [39], Mikulski
et al. [18] disregarded the sulphur constraint, assuming desulphuri-
sation is possible. They increased the DTPO share to 5%vol, adding
it to FAME/DF blends and to rapeseed SVO (cold-pressed and fil-
tered) blends with DF, mixed at different ratios. The aim was to
find an economically feasible fuel needing only limited processing
and with major shares of renewables. A detailed characterisation
of the different blends can be found in Table 7. The flash point
of all the blends was close to that of EN 590 diesel. The addition
of 5% DTPO greatly improved viscosity (by 20%-50%, depending on
the amount of biocomponent) although it was still well above EN
590’s requirement. The parameters, however, were still considered
suitable to operate modern diesel engines and so the samples were
subjected to engine tests focused on analysis of combustion and on
their full emission and efficiency profiles [39,41].
One of the newest methods used to improve fuel characteristics
involves nano-additives. Nanoparticles of titanium dioxide (TiO2 )
can reduce pollutants such as NOX and SOX [204]. The effects of
those additives were already confirmed by Fangsuwannarak and
Triratanasirchai, who tested blends of palm biodiesel with fossil
diesel and 0.1% or 0.2% addition of TiO2 . [205]. The TiO2 addition
contributed to the reduction of kinematic viscosity of different fu-
els blends. Results of tests using an automotive engine showed that
nanoparticles improved combustion completeness. Jeyakumar et al.
[203] analysed the effect of calcium carbonate and titanium diox-
ide nano-additives on a mixture of 20% TPO with 80% DF. They
noted slight decreases of viscosity and density, but greater reduc-
tions of cloud and pour points. The flash point and cetane number
both increased.
25
Progress in Energy and Combustion Science 85 (2021) 100915
The overall fuel properties obtained by TPO/DTPO blending dif-
fer significantly, depending on the share and quality of the individ-
ual components (bio and synthetic). However, from the above dis-
cussion it is possible to make the general observation that pyrolytic
oils and biofuels seem complementary in terms of their proper-
ties. This relates mostly to viscosity (too high for biofuels) and
flash point (too high for TPO). This complementary relationship
also holds true, albeit to a lesser extent, to heating value (lower
energy density of biofuels can be compensated by TPO) and den-
sity. Note that almost none of the authors considering a high bio
component share or a high TPO share in diesel (above 50%) was
able to demonstrate full compliance with EN 590. Nevertheless, the
synergy of pyrolytic oils and biofuels, along with favourable results
achieved through addification of TPO with active particles, suggests
that future renewable liquid fuel research should focus on multi-
component mixtures. Using multiple components adds complexity
but addresses the feedstock availability issue.
4. Engine tests
There is a handful of engine research results involving TPO but
it is difficult to draw firm conclusions about how TPO impacts
combustion, performance and emissions. This ambiguity stems
from the variation in the tested engine platforms, operation con-
ditions and control strategies used by different authors. Addition-
ally, differences in feedstock quality, pyrolysis conditions and post-
processing also add unwanted variables because they influence
TPO’s combustion properties and its propensity to produce toxic
exhaust compounds. Finally, TPOs can be admixed to different base
fuels, along with other additives, creating binary, ternary or even
more complex blends. We have attempted to use a systematic ap-
proach to this complex issue, presenting a summary of the most
important findings which, in our opinion, form the best thinking in
this field. It starts with the effects of mixture formation on com-
bustion, and then deals with emissions. Additionally, results ob-
tained from different engine platforms and for raw TPO, DTPO and
more complex blends are separated in order to provide a reliable
benchmark in each major sub-category of influential factors.
4.1. Mixture formation and combustion
As far as we can ascertain, there are no studies specifically fo-
cused on TPO spray development, atomisation and mixture forma-
tion. Therefore, spray behaviour of TPO and its blends can be only
qualitatively assessed based on engine test results and explained
via the fuel’s physical properties.
In conventional diesel combustion, some portion of fuel evapo-
rates and mixes with air during the ignition delay period. This frac-
tion, dependent on fuel volatility, viscosity and mixing time (gov-
erned by ignition delay) burns as a premixed charge. The remain-
ing, usually much larger fraction, is combusted in a diffusion flame
associated with the developing spray. Crude TPO has low CN, thus
contributing to elongated chemical ignition delay. It also appears to
be more volatile as it has a lower flashpoint. Both factors should
increase the premixed burn fraction, resulting in a more rapid
pressure rise and higher peak temperatures than for DF combus-
tion. These deliberations are generally confirmed by combustion
and emissions studies reviewed in detail below. Note, however,
that optical studies on spray development and mixture formation
are highly recommended to support fundamental understanding of
combustion and emission trends for TPO and its blends.
Tests with crude TPO on basic engine platforms
Basic engine platforms include those that are naturally as-
pirated, without exhaust gas recirculation (EGR) and with low-
pressure mechanical injection systems providing single injection.
Such engines seem obsolete when compared with modern auto-
motive designs, but their simplicity facilitates combustion study at
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
a fundamental level. The limited number of control parameters en-
ables reliable comparison of different research works. All the re-
search platforms included in this review section have a cylinder
bore ranging from 80 mm to 110 mm, typical of light- to mid-
duty, high-speed engines. They share a similar combustion system
design, using direct fuel injection with multi-hole injectors and in-
piston toroidal combustion chamber.
Murugan et al. [173] performed a series of experiments using
a single-cylinder, naturally-aspirated, air-cooled engine with 17.5:1
compression ratio. Fuel was delivered in a single dose, using a
low-pressure mechanical injection system. Experiments were per-
formed at a fixed speed of 1500 rpm and under variable loads,
with fixed start of injection (SOI) timing. Raw TPO was mixed
with DF in fractions of 10%, 30% and 50% vol. It was observed
that increasing the TPO fraction led to a longer auto-ignition delay,
which was attributed to TPO’s higher viscosity, poorer atomisation
and slower vaporisation. More importantly, it was noted that be-
cause of the longer ignition delay of TPO blends, these binary fu-
els were characterised by higher pressure rise rates (PRR), which
was associated with the combustion mode moving from diffusion-
controlled to premixed.
Frigo et al. [179] used a similar experimental platform, but with
a high compression ratio of 20.3:1. The single-pulse, low-pressure
injection was commenced at 12° of crank angle (CA) bTDC. The en-
gine tests were performed at full load and at speeds from 20 0 0
rpm to 3500 rpm. When the TPO content in DF did not exceed 20%,
the combustion process was very similar to that of pure DF. How-
ever, higher fractions of TPO provided substantial delay of auto-
ignition, and additionally rapid increase of cyclic variability, espe-
cially at low engine-speeds. A 40% TPO mixture at 30 0 0 rpm pro-
vided approximately 5°CA delay of SOC when compared to DF. As
with previous studies, a low CN and high viscosity were indicated
as reasons to limit TPO content in DF.
Uyumaz et al. [206] used a single-cylinder, air-cooled, naturally-
aspirated engine with 18:1 compression ratio running at 2200 rpm
with fixed SOI timing at 24°CA bTDC and with variable loads, i.e.
amounts of injected fuel. Comparison of DF and its mixture with
10% of TPO showed that auto-ignition delay was longer for the
TPO blend. Addition of TPO delayed auto-ignition at low loads
by approximately 0.1 ms, which, at the given rotational speed,
translated to 1.3°CA. Differences in SOC diminished as the load
increased.
Chwist et al. [16] also used a basic engine platform, with 16.8:1
compression ratio. The fuel was injected with SOI set to 28°CA
bTDC. Rotational speed was 1500 rpm under fixed, medium load.
As with the above-mentioned studies, the results showed SOC de-
lay with increasing TPO content. Using pure TPO, SOC was delayed
by approximately 8°CA in comparison with DF. The in-cylinder
pressure curves from this study are shown in Fig. 14. This study
also showed that the average SOC demonstrated higher variability,
where ignition timing was highly affected by dropping in-cylinder
temperature [16].
The picture that emerges after analysis of the above studies
shows that low admixtures - up to 20% - of raw TPO in DF can
be combusted in diesel engines without any modifications. SOC is
distinctly delayed at higher TPO concentrations, so most authors
advise advancing injection timing to compensate for increased ig-
nition delay. However, this technique also increases mixing time,
thus moving combustion more towards the premixed mode.
Using a single-cylinder diesel engine with mechanical injection,
Van de Beld et al. [207] found that it would be possible to com-
bust crude TPO provided that inlet-air temperature was increased
to 100-120°C with an engine compression ratio of 17.6:1. Further-
more, if the compression ratio is increased to 22.4:1, the inlet-air
temperature could be reduced by approximately 40°C. The cited
authors also underlined that TPO’s high acidity makes it necessary
26
Progress in Energy and Combustion Science 85 (2021) 100915
Fig. 14. In-cylinder pressure for variable admixture of TPO to DF. Data acquired
at 1500 rpm, medium load, single low-pressure injection, SOI = 28°CA bTDC [16].
Courtesy of Prof. Stanisław Szwaja, Czestochowa
˛ University of Technology.
to substantially modify the fuel injection system to achieve appro-
priate material compatibility.
Tests of DTPO and DF on basic engine platforms
It should be noted that addition of TPO in DF must be limited to
ensure that the final properties of the blended fuel remain within
the specifications set by the relevant standards, especially for au-
tomotive applications. Thus, the studies applied a variety of treat-
ment methods, including distillation and hydrotreatment, to up-
grade the TPO’s properties to enable its blending with DF at higher
ratios. Many authors did not mention the distillation process in
their works, but the viscosity values indicated that purified, light
fractions of TPO were used. Thus, we apply the term DTPO to all
fuels with viscosity within or below the range specified in EN 590
[172].
Kumar Singh and Prabu [208] performed their tests using
a single-cylinder, water-cooled engine with mechanical injection,
where SOI was fixed at 21°CA bTDC. Engine load was varied from
idling to 0.435 MPa of brake mean effective pressure (BMEP) at
1500 rpm. In line with other studies, raising DTPO content in DF
delayed combustion and increased the peak heat release rate (HRR)
when compared with pure DF. However, the higher HRR applied
only until DTPO’s admixture rate reached 75%. With even higher
admixtures the peak HRR was reduced due to a substantial com-
bustion delay of approximately 12°CA. The peculiar effect observed
was that auto-ignition was back advanced at 85% DTPO: the peak
HRR location was between the one for DF and the one for 75%
DTPO. Importantly, end of combustion occurred at nearly the same
location for all tested fuels, from pure DF to the blend with 85%
DTPO.
Żółtowski [13] studied combustion of pure DTPO with DF-like
physical properties in a generator set engine incorporating a legacy
mechanical injection system. The injection timing was set in such
a way that while working on DF, the PRR did not exceed 6 bar/°CA
throughout a range of engine loads from 1.6 to 4.5 bar IMEP.
Switching to DTPO, however, increased PRR significantly at ele-
vated loads. The heat release analysis revealed that physical prop-
erties of DTPO shift the combustion towards a more premixed
characteristic, manifesting by higher heat release rates (refer to
Fig. 15 for details). The effect increased with the fuelling rate
because the auto-ignition delay increased, elongating the mixing
time. Although the applied load range in this study is much below
that of contemporary diesel engines, the observed effects can shed
some light on emission trends discussed below.
Murugan et al. [47,174] performed engine tests with fuels con-
taining large amounts of DTPO, up to 90%. Their experiments were
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 15. Heat release rates for DTPO and DF. Data acquired at 1500 rpm, variable loads expressed by IMEP. Reproduced from [13] with permission from Journal of KONES
Powertrain and Transport, European Science Society of Powertrain and Transport KONES Poland.
Fig. 16. Heat release rates for DF and mixtures of DTPO with DF. Data acquired at
1500 rpm, full load, naturally aspirated, single low-pressure injection, SOI = 23°CA
bTDC. Reproduced from [47] with permission from Fuel Processing Technology, El-
sevier.
performed on the basic engine platform and under the same con-
ditions as described in the previous subsection, for crude TPO
[173]. Note that the viscosity of the DTPO used was half that of DF
and approximately half that used in studies mentioned in the two
previous paragraphs ([13,208]). Increasing the DTPO content to 90%
delayed the initial pre-combustion phase (including cold flames
and negative temperature coefficient reactions) by approximately
2.5°CA This phase is characterised by a minor heat release rate,
visible in Fig. 16 between -30 and -25°CA. The high-temperature
combustion, starting with a characteristic peak resulting from the
premixed phase, remained similar for 90% DTPO and for DF, as ap-
parent in Fig. 16. The discrepancy between this research and other
results discussed in this subsection can be attributed to use of dif-
ferent fractions of DTPO, which had different physical properties. It
is plausible that delayed combustion observed in other works re-
sulted primarily from physicochemical parameters of the fuel, i.e.
lower volatility. Data relating to the DTPO blends used by Muru-
gan et al. [174] are summarised in Table 7.
Tests of TPO-derived fuels and DF on automotive-grade engine
platforms
The studies presented in the previous subsection were intended
primarily to understand TPO’s combustion, whereas the experi-
ments using automotive engine platforms, reviewed in this section,
are rather aimed at verification of TPO as a drop-in fuel.
Martínez et al. [180] performed their research on a modern,
light-duty, automotive engine equipped with turbocharging and
EGR. It also had common-rail (CR) fuel-injection, enabling the au-
thors to apply split fuel-injection. The engine was operated in the
steady states used in the new European drive cycle (NEDC), repro-
ducing loads typical of city driving. The engine was fuelled with
27
Progress in Energy and Combustion Science 85 (2021) 100915
Fig. 17. Heat release rates for DTPO and DF. Data acquired at 2400 rpm, full load,
turbocharged, single injection at 65 MPa, SOI = 1.1°CA bTDC for DF, SOI = 1.5°CA
bTDC for TPO, intake temperature 170°C woIC (without intercooler) and 70°C wIC
(with intercooler). Reproduced from [105] with permission from Fuel, Elsevier.
DF and its mixture containing 5% TPO. The combustion analysis
showed only a negligible increase in combustion duration when
using the TPO admixture.
Vihar et al. [105] used a medium-duty, turbocharged and inter-
cooled engine but with a mechanical fuel-injection system. It was
run at 1500 rpm and 2400 rpm at various loads. The engine was
fuelled with 100% DTPO, distilled to achieve diesel-like fractions.
DF served as a benchmark. To compensate for TPO’s lower CN, the
authors experimented with by-passing the intercooler when fu-
elling with DTPO, thus raising the temperature of the intake air to
help auto-ignition. The results are depicted in Fig. 17, showing how
intake temperature compensated for DTPO’s lower CN. By-passing
the intercooler increased the intake air temperature from ca. 70°C
to ca. 170°C at full load and rated speed, making DTPO’s combus-
tion rate the same as that of DF. However, at lower speeds, al-
though the increase of intake temperature provided the same auto-
ignition timing, the DTPOś combustion was shifted towards a more
premixed, kinetic mode.
Baškovič et al. [14] performed tests on a light-duty automotive
diesel engine with EGR and CR injection system, enabling the use
of split fuel-injection. The engine was fuelled with pure TPO, but
with a viscosity in accordance with EN 590. The authors manipu-
lated the pilot injection timings to compensate for delayed auto-
ignition and the resulting severe HRR of TPO. Diesel-like combus-
tion of pure TPO was achieved by retarding pilot injection by a
few degrees in comparison with the engine’s original control map.
Moreover, the higher the engine load, the larger pilot injection re-
tardation was required.
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 18. Heat release rates for variable admixture of TPO to JME, with DF and pure
JME as references. Data acquired at 1500 rpm, full load, naturally aspirated, single
low-pressure injection, SOI = 23°CA bTDC. Reproduced from [105] with permission
from Fuel, Elsevier.
Tests with TPO and DTPO blended with other fuels
Sharma and Murugan [201] tested different blends of TPO and
JME and DF on a basic engine platform with a single-cylinder, non-
EGR, mechanical injection with a three-hole injector and a com-
pression ratio of 17.5:1. The engine was run at 1500 rpm and at
various loads. SOI timing was set constant at 23°CA bTDC. Pure
JME exhibited shorter auto-ignition delay under these conditions
than the reference DF, due to JME’s higher CN. An admixture of
TPO, with cetane number lower than DF’s, compensated for this
combustion advance. Adding 20% of TPO in JME gave auto-ignition
1°CA earlier than with DF. Adding 30% of TPO in JME gave auto-
ignition 1°CA later than with DF. These results suggest that it could
be assumed that JME with 25% admixture of TPO would provide
auto-ignition properties the same as DF’s. However, differences in
viscosity mean that burn durations and HRR profiles differ, despite
the same auto-ignition timings. So, although JME ignited earlier
than DF, slower vaporisation extended JME’s combustion more to-
wards diffusion mode. Addition of TPO, which also acted as a com-
bustion retarder, resulted in a substantial extension of combus-
tion duration. These effects are clearly visible in Fig. 18, compar-
ing HRR curves for different fuels and their blends. Continuation
of the above work by Sharma and Murugan was aimed at improv-
ing oxidation stability of 20% TPO admixture in JME by addition of
phenolic antioxidants, and at verification of antioxidantséffects on
combustion [17]. The engine’s compression ratio was raised from
17.5:1 to 18.5:1, aiming to tailor the engine parameters to the new
fuel. Some delay of combustion was noted when antioxidants were
added, but not to a significant degree.
Ambrosewicz-Walacik et al. [39] distilled light TPO fraction to
produce a low-viscosity fuel component. This DTPO was then used
to create a ternary blend of 5% DTPO, 40% DF and 55% raw rape-
seed oil. The tests were performed using an automotive diesel-
engine with CR fuel-injection. The tests covered the whole oper-
ational range and included split fuel-injection at low speeds and
single injection at high speeds. Although the engine was operated
using standard calibration, the detailed HRR analyses showed some
specific combustion behaviour of the ternary mixture. Namely, al-
though at split fuel-injection the HRR traces for the mixture were
similar to DF’s, clear low-temperature combustion of pilot fuel was
observed in the case of the ternary mixture. The research was con-
tinued by Mikulski et al. [18] using different blends of the above-
mentioned fuels. All the tested blends included 5% DTPO but had
differing quantities of rapeseed oil, ranging from 20% to 55%: DF
made up the remainder of each blend. The HRR curves for split
fuel injection did not show any significant differences between all
tested blends and pure DF. However, the low-temperature combus-
tion fraction was increasing as the biofuel share rose.
28
Progress in Energy and Combustion Science 85 (2021) 100915
Fig. 19. Regimes of soot and NOX formation on the flame fuel-air ratio and flame
temperature. Redrawn basing on the data in [209].
4.2. Emissions
This section considers the validations of TPO-based fuels in
end-use engine performance from the perspective of emissions. It
aims to shed light on the potential and limitations of using TPO as
an alternative to conventional diesel. As a preliminary remark, it
should be noted that fuel-related exhaust emission trends depend
strongly upon (i) a fuel’s physical properties, which determine in-
jection, atomisation, mixture formation etc., and (ii) a fuel’s chem-
ical properties, which determine auto-ignition timing and combus-
tion chemistry itself. Therefore, both physical and chemical param-
eters should be considered when discussing emissions.
The most problematic species in diesel exhaust are particulate
matter (PM) and NOX . A temperature/fuel-air ratio map (Fig. 19)
helps us to physically-wise understand the paths of their cre-
ation. It shows the soot/NOX trade-off typical of diesel-engine com-
bustion. Concerning NOX , their creation is firstly correlated with
peak combustion temperature (thermal mechanism) and secondly,
with higher local excess air, supporting oxidiser entrainment. Thus,
more premixed combustion generally tends to produce more NOX .
Alternatively, less premixed fuel and limited oxidiser access gener-
ates more soot, because combustion operates with a local oxygen
deficiency. Finally, it should be noted that although the combustion
process always runs along the reaction line presented in Fig. 19, it
is the amount of fuel that undergoes combustion along the indi-
vidual mechanism that determines the emissions.
4.2.1. Nitrogen oxides
There are recognised paths of NOX formation during combus-
tion. The three predominant mechanisms are: Zeldovich (thermal),
Fenimore (prompt) and N2 O (fuel). The first and the last of these
are the prevailing mechanisms in diesel engines [188,210]. Most
NOX in raw diesel exhaust gas is NO, produced mainly in the
boundary layer of the diffusion flame, where the excess air ratio
is nearly stoichiometric, providing favourable temperature (above
1800 K) and access to oxygen. Fuel’s effects on NOX emissions from
diesel engines were extensively investigated when researching var-
ious biofuels and waste fuels. Generally, in the case of the first
generation biofuels (fatty acid esters), much engine research indi-
cated that they led to increased NOX emissions when compared to
DF [211]. In the case of paraffinic fuels, NOX emissions were re-
ported to be lower [3,211]. The review by Bergthorson and Thom-
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 20. Trends in NOX concentrations in exhaust gas for DF and its variable mix-
tures with DTPO. Research on a basic, naturally aspirated engine with single low-
pressure injection, without EGR, full load at variable engine speeds. Reproduced
from [15] with permission from Fuel, Elsevier.
son [211] revealed that NOX emissions from pyrolytic fuels are
roughly half of that from DF. However, this conclusion was based
mostly on research of liquids obtained from biomass, mainly wood.
Tests with crude TPO on basic engine platforms
Murugan et al. [173] performed engine tests without EGR and
with single injection. They found that increasing the TPO content
in DF from 10% to 50% reduced NOX concentration, but only at
low loads: NOX concentration increased at higher loads. This non-
monotonic trend was explained by the fuel’s effect on a combi-
nation of local stoichiometry and temperature. Additionally, it was
pointed out that a higher aromatics content in TPO can increase
propensity to form NOX . Observed trends in NOX concentrations
were correlated with trends in exhaust temperature, which sug-
gests predominating effects of fuel on global stoichiometry. The
trends at low loads were confirmed by Chwist et al. [16]. They
achieved ca. 20% reduction of NOX emissions when the fuel was
changed from neat DF to 20% TPO/DF mixture. Interestingly, NOx
emissions from 100% TPO were double that of neat DF. Combustion
of pure TPO was heavily delayed (refer to Fig. 14), thus giving a
higher premixed fraction and higher bulk combustion temperature.
Tests with refined TPO on basic engine platforms
Rising trends in NOx emissions were not consistent with in-
creasing engine loads when using mixtures containing 20%, 80%
and 90% of DTPO. NOX emissions reduced for higher shares of
DTPO at high loads, whereas there was no significant fuel effect
observed at low loads [47,174]. The discrepancy between these re-
sults indicated that emissions were affected by the reduction in
viscosity (reduced by about 50% via distillation) and the removal
of heavy hydrocarbons. Similar results were achieved by Frigo et al.
[179] on a similar engine platform and using TPO with similar vis-
cosity. Both 20% and 40% TPO samples provided a reduction of NOX
emissions at full load, whereas results were inconclusive at the
medium and low loads.
Doğan et al. [15] used a basic engine platform with mechani-
cal injection system and a fuel dose fixed to the maximum torque.
They found that increasing DTPO content in DF reduces excess air.
NOX concentration increased with DTPO admixture for all investi-
gated engine speeds (Fig. 20). Additionally, the trend was not linear
at low speed (1400 rpm), with rapid increase of NOX concentration
at the highest (90%) admixture of DTPO.
Żółtowski [13] compared DF with neat DTPO and found that
NOX emissions from both fuels were comparable at partial loads.
However, DTPO reduced NOX emissions by ca. 25% at near-idle
regime, but elevated them when operating at high engine-load,
as shown in Fig. 21. Aside from the fact that the NOX levels re-
ported in this study were generally very high (due to the nature of
the legacy engine platform), the observed trends can be explained
by analysing the HRR curves in Fig. 15. For low engine-loads, in-
creased auto-ignition delay did not result in increased peak HRR,
yet retarded combustion reduced peak in-cylinder temperature. On
29
Progress in Energy and Combustion Science 85 (2021) 100915
Fig. 21. Emissions of NOX for DTPO and DF. Data acquired at 1500 rpm and vari-
able loads expressed by IMEP. Reproduced from [13] with permission from Journal
of KONES Powertrain and Transport, European Science Society of Powertrain and
Transport KONES Poland.
the other hand, at high loads, a severe increase in peak HRR greatly
affects the in-cylinder temperature.
Comparison of emission performance of distilled and crude TPO
from the same feedstock was performed by Murugan et al. [212].
They tested DF and its blends containing 30% of TPO or DTPO. They
showed that admixture of TPO did not change emission levels over
the whole load range whereas admixture of DTPO reduced NOX
emissions. Moreover, the difference increased in line with engine
load, with the NOX reduction growing from ca. 10% at near-idle
conditions to ca. 20% at full load.
Recently, Uslu [213] has attempted to optimise a blend consist-
ing of low viscosity TPO and DF, using legacy engine experiments.
The optimised parameters were the blendś proportion of TPO and
the injection pressure. It was found that increasing TPO admix-
ture content above 30% led to a rapid increase in NOX emissions,
whereas TPO’s effect on NOX was negligible when admixture was
below 30%. As could be forecast, NOX emissions fell with reduced
injection pressure, although other emission factors deteriorated.
Tests with TPO-derived fuels on automotive engines
Martínez et al. [180] conducted testing using a multi-cylinder
Euro 5–certified (EGR) engine, exploring different operating points.
He found that 5% admixture of TPO slightly increased engine-out
NOX emissions for all operating conditions, except low loads. This
result contradicted others using similar platforms. Bodisco et al.
[214] used 10% admixture of TPO in DF to fuel a Euro 5 passenger
car with a modern common-rail fuel-injection system, but without
a NOX trap. The tests were realised in real driving conditions which
included equal proportions of urban and rural driving. The authors
showed no significant changes to NOX emissions from fuel to fuel
across the whole cycle, but noted more significant differences at
particular load/speed combinations.
Baškovič et al. [14] used pure DTPO to fuel an automotive
common-rail, direct-injection engine, advancing the pilot injection
to achieve nearly the same combustion course as when using DF.
Comparison of NOX concentrations at similar HRR profiles showed
that DTPO increases emissions by ca. 20%, both at low-load and
high-load conditions, as shown in Fig. 22. After eliminating the
combustion rate effect, it was concluded that DTPO produces more
NOX due to its fuel-bound nitrogen.
Tests of TPO blends with other fuels
Using mixtures of TPO and JME, Sharma and Murugan
[201] identified clear NOX emissions trends, importantly the same
for various engine loads (Fig. 23). Combustion of pure JME pro-
duced ca. 20% more NO than when fuelling with DF. However, in-
creasing TPO admixture from 10% to 50% served to reduce NOX
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 22. Comparison of NOX concentrations in the exhaust gas for DF and DTPO. Re-
search on an automotive common-rail engine with split injection, without exhaust
aftertreatment; 1500 rpm at variable engine loads (80 Nm ≈ 6.4 bar BMEP, 140 Nm
≈ 11.3 bar BMEP). TPO_SH denotes TPO with combustion optimisation by adjusting
pilot fuel injection. Reproduced from [14] with permission from Energy, Elsevier.
Fig. 23. Trends in NO emissions for DF and variable admixtures of TPO in JME. Re-
search on basic, naturally aspirated engine with single low-pressure injection, with-
out EGR. The brake power from 1.1 to 4.4 kW at 1500 rpm corresponds to BMEP
from 1.3 bar to 5.3 bar. Reproduced from [201] with permission from Fuel, Elsevier.
emissions, compensating for JME’s effect. These trends could be
attributed to the opposite physical and auto-ignition properties of
biofuel and TPO. Biofuels ignite earlier but have a higher boiling
temperature, which contributes to mixing-controlled combustion.
TPO has a lower CN, and thus ignites later, but it contains light
fractions which evaporate earlier. Overall, and under most condi-
tions, emissions from combustion of a 50% TPO and 50% JME blend
were a few percent higher than DF’s emissions.
Mikulski et al. [18] used a light fraction of DTPO to reduce vis-
cosity of raw vegetable oil. The test fuels were composed of 5%
DTPO and from 30% to 55% of rapeseed oil, with DF making up
the remainder. Tests were performed using a common-rail automo-
tive engine with standard calibration. There were no differences in
NOX emissions between different fuels and the reference DF at low
loads, but a clear trend was evident at higher loads. The higher the
rapeseed oil content, the higher were the observed emissions. At
the 80% load, the addition of DTPO to the rapeseed oil/diesel mix-
ture was responsible for higher NOX emissions than a comparable
mixture of FAME and diesel.
4.2.2. Particulate matter and smoke opacity
PM consists of insoluble and soluble fractions. Soot and ash
are components of the insoluble fraction; whereas the soluble one
consists of organic carbon, sulphate and nitrate [215]. Soot, which
is a precursor of PM, is intensively created in the first stage of
combustion, typically at the tip of the fuel spray, where a rich mix-
ture is burnt volumetrically and then turns into mixing-controlled
combustion. The production of PM is chemically increased by the
presence of alkynes and polycyclic aromatic hydrocarbons (PAH),
so TPO’s poorer atomisation and high PAH content should lead
30
Progress in Energy and Combustion Science 85 (2021) 100915
Fig. 24. PM emissions including non-volatile and volatile fractions for DF and 5%
TPO admixture. Research on an automotive turbocharged common-rail engine at
selected operating points from a stationary NEDC test (78 Nm ≈ 4.9 bar BMEP, 163
Nm ≈ 10.3 bar BMEP). Reproduced from [180] with permission from Fuel, Elsevier.
to the production of more PM than is the case with DF. Addi-
tionally, it is worth noting that NOX and PM emissions usually
are subjected to a trade-off when combustion shifts between pre-
mixed and diffusion-controlled. More premixed combustion pro-
duces more NOX , whereas diffusion-controlled combustion pro-
duces more PM. Finally, sulphur’s effect on PM creation cannot
be neglected when considering TPO. The sulphur content increases
the mass of sulphates bound in PM, although this effect is not sub-
stantial, because most of the sulphur is converted to SO2 [216].
The majority of available research uses measurement of exhaust
opacity as an indicator of PM concentration. These two parameters
are always correlated in CI engines and enable comparative anal-
yses, although opacity does not provide quantitative information
about PM emissions.
Tests with TPO/DTPO on basic engine platforms
The trends in PM and smoke emissions on engines with single-
pulse injection and in non-EGR conditions are summarised below.
Murugan et al. [173] used blends of DF with TPO admixtures rang-
ing from 10% to 50%. They did not report any significant changes in
exhaust opacity across the whole load range, except at maximum
power, where 50% addition of TPO increased opacity by 7%. How-
ever, the 40% TPO addition slightly reduced opacity compared with
DF. In other works [47,174], the same research group found that
DTPO produces more smoke than DF and they recorded that in-
creasing the proportion of DTPO admixture increases exhaust opac-
ity. Moreover, comparison of emissions from TPO and DTPO 30%
admixtures showed that TPO did not affect smoke emissions across
the whole range of engine loads. At the same time, admixture of
DTPO increased smoke emission by ca. 20%, but only at higher
engine-loads. Fuel effects on PM and smoke emissions were negli-
gible or at least inconclusive at low loads.
Tests with TPO-derived fuels on automotive engines
Martínez et al. [180] performed detailed analysis of smoke and
PM emissions from an automotive engine fuelled with a 5% TPO
blend in DF. At different points of the engine operating map both
opacity and PM emissions were higher with this blend than with
only DF, as shown in Fig. 24. This was attributed to TPO’s higher
aromatics content and also to its poorer vaporisation, due to higher
final boiling point. The measurements of PM emissions were sup-
ported by analysis of particle size distribution. It was found that
the size distributions of both tested fuels were the same at low
loads, whereas under higher loads the distributions for fuel con-
taining TPO shifted towards smaller particles. This was ascribed
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 25. Trends in exhaust gas opacity for DF and variable admixtures of TPO in
JME. Research on basic, naturally aspirated engine with single low-pressure injec-
tion, without EGR. The brake power from 1.1 to 4.4 kW at 1500 rpm corresponds
to BMEP from 1.3 bar to 5.3 bar. Reproduced from [201] with permission from Fuel,
Elsevier.
to TPO’s sulphur and metals contents. Analysis of PM composition
showed that PM generated by TPO contains a higher volatile or-
ganic fraction (Fig. 24).
Tests of TPO blends with other fuels
Measurements of exhaust opacity by Sharma and Murugan
[201] when using blends of TPO with JME show a clear trade-off
with NOX emissions. Compare Figs. 23 and 25 for details. Combus-
tion of pure JME reduced opacity in comparison with DF. The re-
duction was substantial - approximately 30% - at higher loads. In-
creasing TPO content in JME from 10% to 50% gradually increased
exhaust opacity to a level slightly above that when fuelling with
DF. Opacity with 20%-30% admixtures of TPO in JME was compara-
ble to that with DF.
Recent works by Ambrosewicz-Walacik et al. [39] and Mikulski
et al. [18] were aimed at making it feasible to use raw bio-oils in
diesel engines, employing light fractions of DTPO to reduce viscos-
ity. Addition of 5% of low-viscosity DTPO to a mixture containing
40% of DF and 55% of bio-oil produced some reduction of exhaust
opacity. However, a dramatic increase in smoke was observed at
higher engine-loads and with split (pilot and main) injection [39].
This increase was found to be correlated with combustion rates,
specifically advance of auto-ignition. Coupled with the poor atomi-
sation of highly viscous fuel, this resulted in rich combustion, pro-
ducing large amounts of soot. Interestingly, the fuel’s effect on
smoke was much smaller with a single injection of fuel, because
the fuel had less of an effect on combustion rates. Finally, it has
been found that injection strategy strongly affects the emissions
response to fuel type. Further research with the same 5% DTPO ad-
mixture, but with variable amounts of bio-oil and DF, showed that,
in general, ternary fuel reduces exhaust opacity using both single
and split fuel-injection. However, this effect is most noticeable at
moderate load. Moreover, the proportion of bio-oil content did not
show any clear trend in opacity.
4.2.3. CO and unburnt hydrocarbons
Emissions of CO and HC from diesel engines are far less prob-
lematic than NOX and PM [217]. The amounts are small and
these species can be burnt effectively in oxidation catalytic reac-
tors, provided that the exhaust temperature is high enough [218].
Nevertheless, TPO-derived fuels also affect these emissions. This
is mainly due to differences in the physical parameters of fu-
els. Highly viscous fuels have higher liquid fuel spray penetration,
which can result in wall impingement by fuel. This phenomenon
usually produces high amounts of HC because not all the fuel is
burnt during combustion. CO is mainly a residue from incomplete
combustion if the mixture is too rich to oxidise CO at the end of
31
Progress in Energy and Combustion Science 85 (2021) 100915
combustion. The second dominating mechanism, more likely for
diesel engines, is low flame temperature. This can occur when
combustion is delayed towards the expansion stroke or if the fuel
is highly diluted, by recirculated exhaust, for example. CO and
HC emissions trends for TPO-derived fuels and mixtures are sum-
marised here.
Working on a simple engine platform, Murugan et al. observed
that both CO and HC concentrations generally rise with increasing
TPO admixture to DF, independently of engine load [47,173,174].
The increase in CO with addition of TPO was attributed solely
to delayed combustion and thus inhibited CO oxidation. Similarly,
Kumar Singh and Prabu [208] reported an increase of concentra-
tions of both components. The trends in both works appear con-
sistent. Shifting fuel from DF to pure TPO almost doubled CO con-
centration, while the increase in HC content for the same transi-
tion would be approximately 50%. Examples of CO and HC emis-
sion trends from the work by Żółtowski [13] are shown in Fig. 26.
In contrast, Chwist et al. reported a decrease of CO concentration
with increasing TPO content [16]. However, it should be noted that
the baseline CO concentrations reported in this work were already
ultra-high, at 3%. The trend in HC emissions was not monotonic,
but indicated an increase in the exhaust’s HC content when 10% or
more TPO was added to DF. Doǧan et al. [15], using a naturally as-
pirated engine at full load, found that the CO and HC trends were
dependent on engine speed. At low speed (1400 rpm), using a TPO
content of 90% reduced CO by 50% and HC by 20%, when com-
pared to DF. Results were inconclusive at engine speeds beyond
this point.
In the case of TPO mixtures with biofuels, Sharma and Murugan
[201] observed that emissions of both CO and HC when using pure
JME are about 10-20% lower than with DF. Addition of TPO to JME
increased both emissions. The CO and HC emissions were similar to
those from DF when the TPO admixture to JME reached about 30%.
Using a more advanced automotive engine platform, Martínez
et al. [180] evaluated emissions from a 5% admixture of TPO to
DF. They found the admixture increased emissions of both CO and
HC by approximately 10% compared to DF, but only at near-idle
conditions. Differences between the test fuels were negligible at
moderate and high loads. Furthermore, increased emissions of aro-
matics were reported under all conditions and attributed to higher
aromatic content in TPO. Similar results in terms of HC emissions
were achieved by Baškovič et al. [14], although they compared DF
with pure TPO. These results revealed sensitivity to EGR of low-CN
fuels, like TPO.
5. A critical overview and outlook on further research
The last decade has brought an exponential increase of research
into the use of TPO as a combustion engine fuel. However, the un-
clear status of TPO production technology, wide discrepancy in TPO
quality, the different blending strategies and the variety of engine
platforms used for testing all make it difficult to pin down the cur-
rent status of the research. These factors have been reviewed in
Sections 2, 3 and 4. This section’s aim is to distil the knowledge
captured in this review into a concise vision of TPO as a fuel com-
ponent in combustion engines. This is best done by answering the
research questions posed in Section 1.3 of the introduction.
The overview and outlook below provide a focused perspective
on applications for TPO-derived fuels and further research in this
field. This research is most definitely needed if TPO fuels are to be-
come part of a solution capable of solving the sustainability issue
and GHG problem.
What is the current view on TPO well-to-tank environmental
impact and economic feasibility?
On a well-to-tank basis, TPO as a waste-derived fuel is consid-
ered as one of the negative GHG impact solutions. Taking account
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Fig. 26. Emissions of CO and HC for DTPO and DF. Data acquired at 1500 rpm and variable loads expressed by IMEP. Reproduced from [13] with permission from Journal of
KONES Powertrain and Transport, European Science Society of Powertrain and Transport KONES Poland.
of the added value to the circular economy, the net GHG footprint
is assessed on a level of -0.9 to -1.6 kgCO2 e/kg of CO2 removed
from the environment [138,219]. On the gross basis, the well-to-
tank CO2 emission of TPO production is of an order of magnitude
smaller than that of first-generation biofuels. In this respect, TPO
surpasses both SVO and FAME/HVO derived from bio-oils. Taking
into account engine compatibility issues and the extent of process-
ing required to satisfy this compatibility, TPO is also GHG- superior
with respect to popular waste-derived biofuels (TME, UCOME). The
present study implies gross well-to-tank GHG emission of TPO on
an average level of 3.76 g CO2 e/MJ, a value comparable to bio-oil
extraction alone.
The increasing social impact of GHG emission has a pronounced
influence on the fuel market. As shown in this study, currently
most waste-derived fuels and feedstock command market prices
that are similar to or higher than first-generation SVOs and FAMEs.
TPO still stands apart from this trend. With a stable average market
price of $350/10 0 0 kg – a figure almost unchanged over 10 years
– it is roughly one third of the price of all the mentioned biofuels
and it is price competitive with gasoil. This creates an opportunity
for TPO to be accommodated by markets that traditionally cannot
afford expensive fuels and thus struggle to compete with the likes
of automotive and aviation sectors when seeking sustainable al-
ternative fuels. Recent analysis shows that these two markets cur-
rently account for over 90% of all liquid biofuel availability [220].
It must be acknowledged that TPOś low market price is partly a
consequence of a relatively low global demand for this fuel. If this
is about to change in the current energy transition period, cou-
pled with scaling-up the production, the future price-availability
balance of TPO is still unknown.
Adding to the list of uncertainties is the overall environmen-
tal and economic feasibility of TPO production. Though available
LCA studies on TPO indicate that pyrolysis is currently one of the
ecological and net beneficial ELT management routes, we currently
lack any reliable comparative LCA with other sustainable fuel al-
ternatives. This is a serious knowledge gap. The authors´realistic
view of the overall financial feasibility of fuel production-oriented
tyre pyrolysis is inconclusive because of the uncertain future of
TPO’s market price, unfavourable ELT management legislation and
the lack of up-to-date, quality studies on the economics of large-
scale pyrolytic plants. It should be noted that the common opinion
that tyre pyrolysis is not commercially feasible mainly stems from
several big implementation projects from the 1980s and 1990s.
Against the backdrop of the current energy transition, this view
has to be reconsidered.
As a final critical note, it is fair to point out that the mentioned
knowledge gap on TPO’s LCA and economics does not mean that
32
Progress in Energy and Combustion Science 85 (2021) 100915
the number of works available on the topic is lacking. In fact, it
is the reliability of the studies, which in many cases are based on
biased assumptions, that has been found to be questionable.
What is the progress in pyrolysis technology with respect to
maximising the TPO yield and resulting fuel quality?
The review has shown a rapid emergence of research-grade,
pilot-scale tyre pyrolysis plants. The demonstrators are gradually
moving towards more advanced designs, including whole tyre py-
rolysis [75]. Process temperature is considered the most critical,
and the most investigated, optimisation parameter here. The best
results in terms of TPO yield, calorific value and minimised energy
input typically are reported to come in the temperature range of
450-650°C. Further elevation of the temperature not only demands
greater energy input but the intensified rubber cracking results in
more high-volatility hydrocarbons transferred to the gaseous frac-
tion, reducing the TPO yield. Furthermore, elevated temperatures
lead to undesirable increases in TPO’s viscosity and density, as well
as its sulphur and aromatics content. Turning to TPO yield, the
most frequently reported maximum TPO yield is 50%wt. (based on
median from Table 2 / Table A1) but the state of the art is cur-
rently reported to be up to 60% on the mass basis, when coupled
with high heating values (based on median from Table 6: HHV = 43
MJ/kg, LHV = 41 MJ/kg).
Notably, even without specific reactor optimisation, the CN of
TPO meets the US on-road fuel standards as well as all standards
for off-road and marine fuels. Achieving viscosity and density val-
ues that are within EN 590 limits does not pose a challenge, yet
must overcome the trade-off with the fuel’s flashpoint. TPOś high,
diesel-like oxidative stability is another of its quality advantages
as fuel. Crude TPOś properties do not deteriorate significantly with
time, which is a common issue for most biodiesels. Hydrolysis and
microbial growth do not pose additional problems for TPO, assum-
ing the feedstock or end product are properly dehydrated.
However, there are fuel quality challenges for TPO, notably high
sulphur and polyaromatic hydrocarbons contents and potential
acidity issues. In the light of tightening global legislation, sulphur
content is by far the biggest and most immediate challenge for di-
rect applications of TPO as an automotive fuel. Typical sulphur val-
ues for crude TPO produced in an optimised reactor are in a range
of 0.3 -1.0%, although figures below 0.01% were also noted for hy-
drogenative pyrolysis. This means desulphurisation is vital for any
automotive application where EN 590’s 0.001% sulphur limit ap-
plies, even if blends are considered. TPO’s route to marine applica-
tions looks easier, with the IMO global and ECA sulphur caps set
at 0.5% and 0.1% respectively. The high content of PAHs poses a
challenge due to genotoxicity and carcinogenicity, as well as the
propensity to form soot. This issue, as well as the sulphur content
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
and the flash-point/viscosity trade-off, can be partially solved by
TPO-upgrading, as summarised in the next subsection.
In terms of TPO acidity, the results so far are inconclusive.
Reports vary from diesel-like acidity to values that are 10 times
higher than the current automotive standards. Obviously, acidity,
as well as other chemical properties of crude TPO, depends on
pyrolysis conditions, yet this dependency has not been sufficiently
studied.
This brings us to the general knowledge gap in the field
of tyre pyrolysis technology. An observation from this review is
that most applied researchers studying how best to produce TPO
are focusing on a single process parameter, such as temperature,
without considering the underlying mechanisms and parameter
cross-influences. Equally, there are many excellent fundamental-
level studies on mechanisms of tyre pyrolysis which lack the ap-
plied perspective towards optimising TPO quality as fuel. Notably,
achieving optimum TPO yield and composition depends not only
on process temperature and on reactor type and its mechanical pa-
rameters, but also on rubber particle size (from powder to whole
tyres), inert gas flow and many other factors. On a more funda-
mental level, all these variables come down to the mechanisms
of transient heat transfer to the rubber elements, gas diffusion
through the solid material and gas retention time before cool-
ing and condensation. Therefore, elaboration of thermodynamic
and gas flow models, combined with solid decomposition and gas
chemical kinetics would enable understanding of the discrepan-
cies between experimental studies, and thus reduce global applied
research effort. As well as the need to connect fundamental and
applied-level research, comes a need for research to investigate
multi-parameter optimisation of reactor operation.
Finally, among the open research fronts is investigation of co-
pyrolysis of tyres with biomass. This is a relatively new con-
cept, so the number of available works on this topic is limited
and scattered over different feedstock configurations. The syner-
gistic effects seem evident, yet not sufficiently understood. The
research trajectory, however, seems very important from the per-
spective of achieving high-quality fuel, increasing the oil yield and,
at the same time, tackling the availability limitations of sustain-
able/renewable feedstocks.
What are the available TPO-upgrading technologies and what is
their effect on the end-fuel quality?
Assuming the pyrolysis itself is fairly well optimised, crude TPO
has the potential to fulfil the requirements of marine and of-road
fuel standards. Automotive fuel regulations can be met, except in
terms of the aforementioned viscosity/flashpoint trade-off and the
sulphur content. Thus, when starting with a relatively high qual-
ity of crude oil, it is probably not economically feasible to ap-
ply refinery-grade cracking processes, such as hydrocracking, for
instance. Indeed, those processes have not been widely demon-
strated with TPO and, according to available literature, refinery-
grade sulphur removal (HDS) is deemed to be hardly effective
when considering the constraints of automotive fuel market re-
quirements. It is worth noting that the 2016 EU-project SULFREE
attempted to combine state-of-the-art microwave pyrolysis with
refinery grade hydrotreating, yet failed to achieve TPO with sul-
phur levels below 0.1% [221].
Considering the above, the future TPO-upgrading technologies
will most probably orient towards infrastructurally low-cost solu-
tions, suiting the trend in distributed TPO production with low-
volume reactors with capacity to process 10 0-20 0 tonnes per day
of ELTs. On the basis of that scenario, this review identified two
main low-cost desulphurisation processes for TPO: fractional dis-
tillation and extraction using ionic liquids.
Many different strategies of TPO fractionation have been tested
while attempting to achieve fuel properties within EN 590 limits. It
has to be said that none is completely successful. Fractional distil-
33
Progress in Energy and Combustion Science 85 (2021) 100915
lation of TPO, yielding DTPO, generally offers regulation of viscosity
and cold properties. Accurate fractionation supports the removal of
PAHs, which have high boiling points. The desulphurisation effects
achieved by distillation vary from study to study. Application of
ionic solutions for liquid-liquid extraction was also demonstrated,
showing potential to halve sulphur content on average. Bearing
in mind that the addition of an in-reactor catalyst helps to opti-
mise pyrolysis, and that a TPO sulphur level below 0.01% has al-
ready been achieved, further progress towards TPO fuel applica-
tions seems feasible, if fuel blending is considered.
Ultimately, providing a direct quantitative answer to the ques-
tion regarding achievable fuel quality by application of different
upgrading technologies seems impossible at this moment. This per-
tains to the knowledge gap similar to one related to TPO produc-
tion, described in the previous subsection. Namely, the research di-
rected to optimising engine-related fuel properties is so far, in the
great majority of cases, performed without a basic chemical back-
ground and analytical support. In contrast, the fundamental-level
research on TPO fractional analysis lacks the targeted context of
achieving superior engine-fuel properties. For example, trade-offs
between viscosity and flashpoint implied by some researchers for
DTPO can be avoided if distillation curve analysis is used to per-
form targeted fractionation.
What is TPOs potential as a fuel component?
Although progress in desulphurisation techniques and develop-
ments in pyrolysis process control is improving its quality, TPO’s
most feasible application is probably not as a stand-alone fuel.
Blends are the favoured route, not only because they facilitate the
improvement of the end-fuelś properties, but also from the per-
spective of availability. No single alternative fuel, such as waste fu-
els, biofuels or synthetic electro-fuels, will be capable of becoming
a full substitute for all fossil diesel. Blending with diesel or heavy
fuel oils is the obvious strategy here.
A promising route for TPO-derived fuels is to take advantage
of their complementary properties with biofuels. Biofuels usually
suffer from high viscosity (FAME) or poor lubricity (HVO) yet offer
substantial reserves in terms of flashpoint and CN. TPO/DTPO has
the opposite characteristics. Another potential route for non-road
applications of DTPO, especially in developing countries, might be
to use its light fractions as an effective viscosity improver when
raw vegetable oils are admixed to diesel. This was demonstrated
by Mikulski et al. [18]. It was also pointed out in the literature
[17] that TPO can offer an additional benefit in biofuel blends be-
cause it improves storage stability when mixed with FAME.
Fuel blending is at the bridge of fuel-engine research and the
major issue with the current situation comes from the fact that
research in this field is mainly performed by applied engine re-
searchers. They often try to find the right way to use TPO by pick-
ing from a wide range of possible blending strategies, but inves-
tigate routes that could be immediately ruled out with a better
consideration of differences in chemical make-up. More complex,
tailored blends should be explored. This fuel blend design chal-
lenge should be supported by the development and use of pre-
dictive models that can target specific properties or engine per-
formance [222]. Development of these models should be strongly
encouraged in order to focus experimental testing and accelerate
the development of sustainable liquid fuels: climate change does
not allow the luxury of time.
How do different fuel compositions of TPO and TPO-derived
fuels perform in the engine in terms of combustion characteristics,
efficiency and emissions?
The review of engine test results reveals several trends. Within
the constraints of the quality of the TPO samples used, small ad-
mixtures of crude TPO (up to 10%) to diesel can be used without
any profound effects on the combustion process and connected ef-
ficiency, while avoiding issues with catalyst poisoning Using pro-
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
cessed (distilled and desulphurised) TPO can further extend this
admixture limit somewhat higher than 10%. At such conditions,
NOX emissions can be slightly elevated, evident only at higher
loads, and CO and HC can increase by approximately 10%, but only
at low loads. Note that these differences in state-of-the-art com-
bustion engines are reported to disappear over the driving cycle
when using low levels of TPO additions.
When combustion effects are neglected, TPOs tend to emit
more NOX due to higher amounts of fuel-bound nitrogen. Greater
CO and HC emissions result from higher viscosity and poorer spray
atomisation, limiting oxygen entrainment. TPO increases PM emis-
sion because of its high aromatic and sulphur contents. Both these
fractions are found to promote PM formation, which in the case
of TPO, usually is composed of small-diameter particulates. These
smaller particles are proven to have a more deleterious impact on
human health. Note, however, that reports documenting quanti-
tative particulate mass or number for TPO combustion are rather
scarce: most authors instead used smoke opacity as the basis for
their conclusions on PM. Opacity was more likely to be influenced
by local mixture stoichiometry.
The abovementioned fuel-related effects on emission can be
scaled with increased TPO fuel content and also can be partially
neutralised by optimum fuel composition. Large-scale TPO admix-
ture makes the effect of the fuelś properties on combustion be-
come more pronounced, in turn influencing emissions to a much
greater extent. Delayed auto-ignition is commonly reported for
TPO or DTPO additions above 20%, shifting combustion towards a
more premixed mode, which usually generates higher peak tem-
peratures, elevating NOX emissions. Long ignition delays also shift
combustion from its optimum timing, and thus impact engine ef-
ficiency. Fuel viscosity and cetane number are primary drivers of
ignition delay. High viscosity is relevant only for non-processed
TPO samples and harms combustion at high-load regimes where
spray formation is the main limiting factor for ignition. TPO’s lower
cetane number is responsible for increased chemical ignition de-
lay manifesting at low loads and at high EGR ratios. Van de Beld
et al. proved that this low CN effect can be successfully mitigated
by elevating the intake-air temperature [207]. This technique al-
lowed the combustion of neat TPO samples with diesel-like char-
acteristics and efficiency. Engine control strategies have also been
demonstrated to mitigate viscosity effects for TPO, including ad-
vancement of injection timing (both main and pilot injection) and
increasing injection pressure. Both strategies are, however, limited
by the threat of spray wall-wetting. Note that viscosity control by
fuel pre-heating is a standard feature in flex-fuel marine diesel en-
gines capable of running on HFO.
Critical evaluation of available research related to engine oper-
ation on TPO reveals a clear lack of reliable information on non-
regulated emissions, even though it is an important issue in the
consideration of new fuels. A notable exception is the work by
Martínez et al. [180], where a multi-compound Fourier transform
infra-red (FTIR) exhaust gas analyser was used. This study, how-
ever, used only 5% TPO admixture to DF, thus the differences in
emissions of most hydrocarbons, except aromatics, were below the
level of significance. Naturally, the aromatics content in exhaust
gas are inherited from fuel composition. The same effect is ex-
pected in the case of sulphur, both in terms of gaseous exhaust
components and PMś chemical composition. There is a need for
detailed emissions speciation when TPO is considered as a fuel
component.
In any observations regarding PM, it is important to point out
once again that most studies considered only smoke opacity: only
a few used PM concentration measurement and sizing. Refer to
[180] for reliable information on PM distribution from TPO.
As a final discussion note, it is necessary to say that construct-
ing this summary of emission trends related to TPO fuels was only
34
Progress in Energy and Combustion Science 85 (2021) 100915
possible by adding the perspective of fuel properties and combus-
tion analysis. The number of works on engine emissions from TPO
that lack this context is, in fact, far greater than those reviewed
in Section 4. Without a combustion perspective, the results from
various works seem contradictory, making it impossible to draw
accurate conclusions. This arouses a general concern that incom-
plete works may lead to conclusions that have a possible negative
impact on the take-up and commercialisation of alternative fuels.
With this rather critical remark, we open the discussion about out-
look.
Outlook on TPO’s perspective
An underlying premise of this research is that waste tyres form
a considerable feedstock for fuel production, comparable to that of
biomass once food production has been prioritised. For instance,
considering the durability of the average car tyres of 70 0 0 0 km
and fuel consumption at a level of 7 dm3 /100 km, a vehicleś own
worn tyres can pay back 0.5% of the total fuel used.
The evidence considered in this review indicates that TPO has
sufficient quality to be used directly as bunkering fuel, though is-
sues with fuel-to-fuel compatibility would have to be resolved.
There is a fairly small gap between the quality of fuel from the cur-
rent state of the art in TPO production technology and the standard
set for automotive diesel fuels. Continued research along the sug-
gested lines should be capable of bridging that gap. To this end, the
research must become more multidisciplinary, merging the funda-
mental expertise in feedstock/fuel chemistry with applied knowl-
edge on pyrolysis technology.
The requirement for sustainability will shift future fuels to-
wards more complex blends accommodating all renewable re-
sources. Feedstock co-utilisation and post-production blending
strategies should be developed to build on the complementary
physicochemical parameters of individual feedstocks and/or fuels.
Blending TPO and FAME/UCOME have been suggested here as a
good example of this complementary approach. Another potential
route is co-pyrolysis of waste tyres and biomass. According to the
present fuel quality and emissions review, an exemplary composi-
tion of 7% FAME / 7% (desulphurised) TPO/DTPO / 86% diesel could
be straightforwardly applied on the market, offering benefits over
the current B7 diesel. Other combinations, for instance, blending
TPO with HVO, also should be explored. Progress here requires
methodological reinforcement in terms of chemical expertise and
predictive tools for modelling blended fuel properties and engine
performance.
Before TPO-derived or any other pyrolytic fuels can be mar-
keted, engine manufacturers must accept them, which in turn,
means that more vehicle and engine tests using TPO blends should
be picked up by research organisations. The bulk of engine test
results with TPO involve legacy (basic) engines. Tests with mod-
ern (EU Stage V/Euro 6) engines are lacking. Furthermore, the twin
threats of PM and PAH are already identified as potential issues,
which in our opinion will limit the application of TPO/DTPO to
blends not exceeding 10%. There are many more pending emissions
issues for TPO applications that have not been addressed at all so
far. Unlegislated emissions need to be considered, especially with
respect to aldehydes and aromatics. TPO is expected to generate
higher levels of both of these, which may lead to imposition of
additional constraints on TPO. Additionally, real driving emission
tests of vehicles fuelled with TPO should be performed. The effect
of TPO fuels on modern exhaust aftertreatment systems has been
hardly studied at all. Sulphur poisoning of diesel oxidation cata-
lysts is an obvious issue here, and there may be others. Catalyst
tests should be conducted in tandem with long-term durability en-
gine tests to check for potential deposit formation (injectors, valves
etc.) and performance deterioration over time.
Finally, it is worth remembering that tyre pyrolysis, although
more economically feasible in the current energy transition pe-
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
riod, lacks legislative incentive to encourage its large-scale up-
take as a clean and efficient way to use waste tyres. Contin-
ued lobbying in this respect is required to transition from sim-
ple (but destructive) incineration of tyres towards more sustain-
able pyrolysis. Furthermore, the above pros and cons of pyrolytic
oil as a fuel component should be weighed against other possi-
ble applications for TPO, such as its use in a closed-loop, tyre-
manufacturing process. This comparison should include factors like
process economy, well-to-wheel CO2 footprint and local availabil-
ity. It should also assess combinations of TPO with other feed-
stock in fuel and tyre producton chains, demanding a complex
decision-making equation. Multi-criteria decision-making using ar-
tificial intelligence-based approaches would allow complex data
from diferent sources to be merged with expert knowledge into
reasoned and unbiased decisions [223,224].
6. Conclusions
The objective of this work was to review the current status of
tyre pyrolytic oil in combustion engine applications. This fills an
important knowledge gap on the sustainability transition roadmap,
because the vision of how to best utilise waste tyres is not clear.
This feedstock, with its substantial availability and good heating
value, can contribute to solving the short-term fuel transition prob-
lem for off-road machinery, heavy-duty road vehicles and marine
transport. This review’s focus was on diesel engine applications be-
cause these are the prime-movers in these sectors.
To this end, this review answers the governing research ques-
tions related to TPO production and quality; post-processing and
quality improvement methods; and engine validation of the fi-
nal TPO-derived fuels. These questions are discussed in detail in
Section 5. Below, we present the main conclusions drawn from the
discussion:
i TPO as waste-derived fuel has a negative GHG impact, removing
up to 1.6 kgCO2 e/kg of waste tyres from the ecosystem. At the
same time, gross GHG emissions of TPO production are three
times lower than those of typical first-generation biofuels.
ii TPOś future availability is comparable to that of vegetable oils
and the average market price of $350/10 0 0 kg makes it the
cheapest sustainable fuel alternative, creating an incentive for
its use as an admixture to marine and off-road fuel supply
chains.
iii The current state of the art in tyre pyrolysis provides average
yields of crude oil of 50%, without any external energy input.
iv With nearly diesel-like lower heating value of approximately 41
MJ/kg., the properties of crude TPO technically enable direct fu-
elling of compression ignition engines.
v The fuel can meet the low-sulphur fuel oil standards for
bunkering fuel and so can be used in all ships subject to the
IMO global sulphur cap (max 0.5% fuel sulphur content) with-
out needing scrubbers. The quality is insufficient for automo-
tive applications governed by the EN 590 diesel fuel standard
or corresponding US norms.
vi New desulphurisation technology, such as the ionic solution
washing process, can reduce sulphur content below 0.1%. The
process is not infrastructurally demanding and supports the
economics of distributed TPO production.
vii TPO viscosity can be tailored using distillation, but the trade-
off between viscosity and flash point should be considered.
Fractional distillation should be targeted at a narrower boiling
range than currently exploited to avoid this trade-off.
viii The limitations of viscosity, flash point, sulphur content and
polyaromatic hydrocarbons fraction narrow down automotive
applications of TPO/DTPO to low-level blends (up to 10%) with
mineral diesel and other fuels. Mixtures including DTPO and
35
Progress in Energy and Combustion Science 85 (2021) 100915
FAME (or crude bio-oils) are most feasible since these fuels can
be compatible in viscosity, flash point and cold properties.
ix Emissions are an important constraint for TPO fuel applica-
tions. Its combustion-related effects can be mitigated either by
matching fuel properties or combustion control, but TPO is fun-
damentally prone to emit more nitrogen oxides, CO, unburnt
hydrocarbons and particulates than diesel fuel. However, for
typical blends containing up to 10% TPO, the effects are rather
small and also diminish at transient engine operation under
real driving conditions.
x A major concern of using TPO is associated with particulate
emissions, which scale up linearly with TPO content in the fuel.
The size distribution of the PM, and TPO’s substantial polyaro-
matic hydrocarbons content, which translates to PMś chemical
composition, are also problematic due to their carcinogenic na-
ture.
xi Despite the above issues, the major hurdle for TPO remains the
waste tyre management legislation. Regulations in this sphere
fail to provide the necessary incentive for pyrolysis to compete
successfully with incineration. The economic and ecological fea-
sibility of TPO needs to be rigorously re-evaluated in the con-
temporary context of energy transition.
xii The present work puts forward the necessity of professionalisa-
tion of research in the field of TPO. Current infrastructural and
methodological commitment to this issue is too low when com-
pared to other fuel alternatives. Future endeavours should ulti-
mately become more multidisciplinary to address the apparent
disconnect between fundamental level research and TPO appli-
cations.
The above conclusions, complemented by exact numbers in the
adjoining discussion, aim to provide an unbiased input to help
shape the future fuel roadmap for TPO. Accordingly, these conclu-
sions do not pre-judge the outcome of such work and so they do
not convey a final decision. That decision-making process should
weigh TPO against different feedstocks available for sustainable
fuel production, and also against possible competing applications
of these feedstocks.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgments
The authors acknowledge expert support from Dr. Katriina
Sirviö (VEBIC Fuel Laboratory, University of Vaasa, Finland) and Dr.
Kamil Duda (Fuel Laboratory, University of Warmia and Mazury,
Poland). Their critical views were invaluable during the prepara-
tion of the manuscript and its revision.
We would like to thank David Wilcox for his help in proofread-
ing the manuscript and engaging his expertise in polishing our pa-
per.
Jacek Hunicz and Maciej Mikulski acknowledge financial sup-
port from the project Lublin University of Technology-Regional Ex-
cellence Initiative, funded by the Polish Ministry of Science and
Higher Education (contract no. 030/RID/2018/19).
Appendix. Type of reactors used during pyrolysis and most
relevant process conditions affecting TPO yield
Table A1.
 Table A1
Type of reactors used during pyrolysis and most relevant process conditions affecting TPO yield

Reactor type Reactor Process Feed material Feed Rate Inert gas / flow Temperature TPO Yield [%] Conditions for Reference Manuscript objective
volume rate range [°C] optimum TPO yield
[dm3 ]

fluidized bed 0.9 continuous shreds (1.4-2.3 mm) 0.2 - 0.5 kg/h N2 + air 700-880 25-38 700°C, feed rate 0.3 [77] Process evaluation
kg/h
n.a. n.a. ground n.a. N2 450-800 n.a. n.a. [48] Process evaluation
n.a. fast pyrolysis shreds (1-2 mm) 1 kg/h N2 /steam 500-600 51-65 500°C [78] Product analysis
n.a. n.a. ground 5 kg/h steam 360-810 30-50 450°C, 0.32 mm [79] Process evaluation
particle size, short
gas residence
n.a. n.a. shreds (0.8-1.6 mm) 3 kg/h N2 /pyro 600-700 over 36 600°C, short gas [80] Process evaluation
gas/steam residence
n.a. continuous, fast shreds (0.3-1.18 0.6 - 1.5 kg/h N2 350-600 25-45 400°C, particle size [81] Process evaluation
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.

pyrolysis mm) 1 mm, feed rate

0.78 kg/h
0.23 fast, porous co-pyrolysis 0.2 kg/h N2 (0.25 400-650 n.a. n.a. [82] Product analysis
catalysts (zeolites) dm3 /min)
4.1 continuous, fast sherds (3-4 mm) n.a. N2 350 26-38 400-450°C [83] Process evaluation
pyrolysis
n.a. intermittent (4-60 ground, steel and n.a. H2 375-425 42-47 375°C, reaction [84] Product analysis
min) fabric free time 4 min.
fixed bed 1.5 intermittent (15 ground, steel free 0.05 kg/run He (0.2 350-550 30-38 550°C [85] Process evaluation
min) dm3 /min)
1.2 intermittent (60 shreds (1.0-1.4 mm) 0.2 kg/run N2 process 35-56 430°C, zeolite [65] Process evaluation
min), microporous constant 500 ZSM-5 catalyst
catalysts (zeolites) (430-600

36
catalyst)
0.4 intermittent (60 shreds (2.0 mm) 0.01 kg/run N2 (0.1 375-500 46-60 425°C [70] Process evaluation
min), perlite dm3 /min)
catalyst
3.5 intermittent (30 strips (2-3 cm 0.2 kg/run N2 (1 dm3 /min) 300-700 5-39 700°C [86] Product analysis
min) wide)
2.2 intermittent (120 shreds (1-2 mm), 0.05 kg/run N2 (2 dm3 /min) 500-800 30-38 500°C [87] Product analysis
min) steel and fabric free
0.59 intermittent (60 shreds (1.5-2 mm), 0.13 kg/run N2 (0.025 550-800 47-56 n.a. [88] Process evaluation
min) steel and fabric free dm3 /min)
0.95 intermittent (120 shreds (20 mm) 0.3 kg/run N2 (0.4 400-700 30-43 500°C [51] Product analysis
min) dm3 /min)
0.004 intermittent (15 ground 0.001 kg/run N2 (0.15 400-600 36-45 n.a. [89] Product analysis
min) dm3 /min)
2.1 intermittent (50 cross section 0.8 kg/run N2 (2 dm3 /min) 375-575 up to 49 475°C [90] Fuel production
min)
0.08 intermittent shreds (<3 mm) 0.01 kg/run n.a. 850 20-58 n.a. [91] Process evaluation
1.7 n.a. shreds (1-2 mm) n.a. N2 (5 dm3 /min) 500-800 33-41 n.a. [92] Product analysis
6.7 intermittent (160 shreds (10-50 mm), n.a. N2 330-380 38-88 n.a. [93] Fuel production
min) steel and fabric free
n.a. intermittent (20 shreds (1-1.6 mm), n.a. N2 (0.5- 1.5 400-500 41-53 450°C [94] Fuel production
min) steel and fabric free dm3 /min)
2.8 intermittent (15 shreds 0.25 kg/run n.a. 400 25-55 n.a. [95] Fuel production
min)
179 intermittent shreds 20 kg/run N2 300-500 30-42 400°C [96] Process evaluation
0.5 intermittent shreds (10-30 mm) 0.2 kg/run N2 (0.1 550-800 45-65 400°C [10] Product analysis
dm3 /min)
(continued on next page)
Progress in Energy and Combustion Science 85 (2021) 100915
 Table A1 (continued)

Reactor type Reactor Process Feed material Feed Rate Inert gas / flow Temperature TPO Yield [%] Conditions for Reference Manuscript objective
volume rate range [°C] optimum TPO yield
[dm3 ]

moving bed 0.15 continuous shreds (2 mm) 6 kg/h N2 (1.2 600 54 n.a. [97] Process evaluation
dm3 /min)
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.

n.a. continuous shreds (5 mm), 3.5 - 8 kg/h N2 (0.2 600-800 28-48 n.a. [98] Process evaluation
steel and fabric free dm3 /min)
vacuum 0.1 intermittent shreds 0.1 kg/run -4 kPa vacuum 450-600 33-50 480°C [69] Process evaluation
n.a. intermittent shreds (6-13 mm) 1 kg/run -3 kPa vacuum 240-500 10-55 415°C [99] Product analysis
848 continuous n.a. 19 kg -13 kPa vacuum 500 50 n.a. [100] Fuel production
848 continuous n.a. n.a. -80 kPa vacuum 480-500 n.a. n.a. [101] Product analysis
n.a. intermittent shreds 1 kg/run -70 kPa vacuum 500 n.a. n.a. [102] Product analysis
848 n.a. shreds / whole tyres n.a. -10 kPa vacuum 480-520 43-56 n.a. [103] Fuel production
n.a. n.a. n.a. n.a. n.a. 400-600 30-53 n.a. [104] Process evaluation
n.a. n.a. n.a. n.a. n.a. 500-700 n.a. n.a. [105] Fuel production
40640 intermittent shreds 10000 kg/run n.a. 40-45 n.a. [106] Fuel production
not specified n.a. intermittent (30 ground 0.004 kg/run N2 (0.075 350-700 18-56 550-575°C [107] Process evaluation
min) dm3 /min)

37
n.a. n.a. rubber wastes from n.a. He (0.1 n.a. n.a. n.a. [52] Product analysis
tyre production dm3 /min)
n.a. intermittent (60 n.a. n.a. N2 (0.025 500 n.a. n.a. [108] Process evaluation
min), Pt-supported dm3 /min)
catalysts (zeolites)
n.a. intermittent (180 ground 0.04 kg/run N2 (0.03 400-600 28-41 400°C [109] Product analysis
min) dm3 /min)
spouted bed 11.2 continuous ground, steel free 0.2 kg/h n.a. 425-600 44-55 n.a. [110] Product analysis
n.a. continuous shreds (2.8-3.3 0.1 kg/h n.a. 425-575 54-58 n.a. [58] Process evaluation
mm), steel and
fabric free
28.3 intermittent, ground, steel free n.a. n.a. 450 40 n.a. [71] Fuel production
catalysts (zeolites)
0.16 intermittent (90 ground, steel and 0.12 kg/run H2 450-600 10-37 550°C [111] Product analysis
min), catalysts fabric free
(zeolites)
rotary (auger) n.a. continuous shreds (1-2 mm), 0.3 kg/h N2 500-600 39-51 n.a. [112] Process evaluation
reactor steel and fabric free
n.a. n.a. shreds (5 mm), n.a. n.a. n.a. n.a. n.a. [113] Fuel production
steel free
Progress in Energy and Combustion Science 85 (2021) 100915
M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
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M. Mikulski, M. Ambrosewicz-Walacik, J. Hunicz et al.
Maciej Mikulski (PhD) is an associate professor in com-
bustion engine technology at the University of Vaasa, Fin-
land and a Principle Scientist in the VEBIC internal com-
bustion engine laboratory (Finland). He has 14 years of
professional experience in combustion engine research in-
volving alternative fuels in industry and academia. He
has worked in several relevant engine/fuel development
projects with the world’s leading automotive, marine and
off-road OEMs and co-established the first full-load ca-
pable, ultra-efficient RCCI natural gas engine. For his re-
search on low temperature combustion, he was recently
honored with the Finish Ostrobothnia Chamber of Com-
merce award. He is an author of over 80 research papers
in the field and a member of several international expert groups and combustion
research associations. He is currently (2020-2023), amongst others, a leader in 2
major (over 25M€ in total founding) Finish Industry-Academia consortia the CLEAN
PROPULSION TECHNOLOGY and SILENT, both committed to advanced combustion
and powertrain development.
Marta Abrosewicz Walacik (PhD) is a professional
chemist and a former head of the Biofuel Laboratory at
the University of Warmia and Mazury in Poland. Since the
beginning of the carrier, she has focused on tyre pyroly-
sis and fuel upgrading. Over 35 published research papers
involve research on TPO, FAME and crude oil refining for
different applications, including combustion engine fuels.
She is responsible for critically assessing the analytical
works related to this review and gathering the informa-
tion on the state of the art in pyrolysis process.
42
Progress in Energy and Combustion Science 85 (2021) 100915
Jacek Hunicz (PhD, DSc.) is an associate professor and
head of Powertrains Laboratory at the Lublin University
of Technology, Poland. His track record includes experi-
mental engine research and renewable low-carbon fuels.
In the area of combustion research, his studies are cen-
tered on the control strategies for low-temperature com-
bustion in HCCI engines, including the NVO fuel reform-
ing. With over 23 years of professional expertise in com-
bustion engines and powertrain development, prof Hunicz
is a grant holder of several relevant nationwide projects
funded by the Ministry of Science and Higher Education
and National Science Centre. He is a member of several
international research groups. He is also an innovation
consultant for domestic off-road vehicle and bus manufacturer Ursus and techni-
cal advisor to the Polish military industry in the field of powertrain testing. Since
2018, he has been a board member of the Polish Scientific Society for Combustion
Engines.
Szymon Nitkiewicz (PhD) obtained Master’s degree in
Mathematics and graduated a PhD in Biocybernetics
and Biomedical Engineering. He is an owner of several
Patents, awarded at international exhibitions. His expe-
rience in mathematics allows him to analyze in detail a
wide range of issues. As part of Dr. Ambrosewicz’s team
he specializes in assessing the impact of technology on
human health and supports the current work with his
critical outlook in this respect. His scientific interests os-
cillate in topics related to supporting medical diagnostics,
as well as in assessing the impact of human activity on
the environment. He is a member of the project team In-
tereg Baltic Sea Region financed by the EU.