Fuel 185 (2016) 236–242

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Physico-chemistry properties of fuel blends composed of diesel and tire

pyrolysis oil
Erick Ryoiti Umeki, Camilla Fernandes de Oliveira, Ricardo Belchior Torres, Ronaldo Gonçalves dos Santos ⇑
Chemical Engineering Department, Centro Universitário FEI, São Bernardo do Campo, SP 09850-901, Brazil

h i g h l i g h t s

Alternative fuel produced by pyrolysis of scrap tires encompasses high content of hydrocarbons.

Tire pyrolysis oil was mixed with petroleum diesel for producing fuel blends.

Pyrolysis oil/diesel blends showed properties that enable them to be applied as fuel.

Blend properties highlight the complexity of the chemical interactions between the fuels.

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

Article history: Pyrolysis of scrap tires has been pointed out as an alternative to the incorrect disposal of tire wastes.
Received 10 June 2016 Pyrolysis processes can produce tire-derived oils that may be used as fuel or added to conventional fuels,
Received in revised form 18 July 2016 producing fuel blends with improved properties and reduced cost. The pyrolysis process can contribute to
Accepted 22 July 2016
remove tire residues of inadequate sites and it can be a sustainable process to produce alternative fuels.
In this work, the properties of blends between petroleum diesel and pyrolytic oil obtained from the ther-
mal degradation of tire waste were investigated.
Keywords:
The liquid obtained from the tire waste pyrolysis was black oil, possessing a distinctive, unpleasant and
Tire waste
Pyrolysis
strong odor. The compositional analysis of pyrolytic oil describes the liquid as a complex mixture, com-
Fuel blends posed mainly of aromatic compounds and olefins. The oil specific gravity was 0.93 g cm3, while gasoline
Pyrolysis oil and diesel showed 0.74 and 0.84 g cm3, respectively. The Research Octane Number (RON) for the pyro-
Diesel lytic oil was found to be similar to the RON for Premium gasoline (higher than 100). Its Motor Octane
Energy Number (MON) was found to be slightly lower than the MON for gasoline and very higher than those
Sustainability to diesel fuel. The pyrolytic oil showed also higher detonation resistance in relation to the conventional
fuels investigated. The oil has the High Heat Value (HHV) in-between than that for gasoline and diesel
fuel, achieving 42 kJ g1. The tire pyrolysis oil was miscible with diesel in the entire concentration range.
Pyrolysis oil/diesel blends showed properties that make them able to be applied as fuel. However, blend
properties highlight the complexity of the chemical interactions between the fuels, which need consid-
eration before their applications.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction processes besides petroleum. The use of alternative energy sources

Over all the global demand for fuels has been supplied mainly
by non-renewable resources deriving from petroleum distillation
[1]. The industrial process for obtaining these resources has a
strong impact on the environment, promoting ecological damage
and impairment to human health. Extensive effort has been
devoted to the production of fuels from other sources and
⇑ Corresponding author at: Chemical Engineering Department, Centro Univer-
sitário FEI, Avenida Humberto de Alencar Castelo Branco 3972, 09850-901 São
Bernardo do Campo, SP, Brazil.
E-mail address: rgsantos@fei.edu.br (R.G.d. Santos).
has been an option for reducing the use of fossil fuels.
The most promisor materials for the fuel production are indus-
trial by-products and biomass wastes, among which stand out the
sugarcane bagasse, coconut fiber, corn cob and cotton waste [2]. In
some emergent countries, biomass has accounted for about a third
of the energy consumed [3]. The wide availability of scrap tires
caused by increasing the number of petrol-powered vehicles in cir-
culation has driven the use of tire waste as an alternative energy
source. In the 1990s, the annual waste tires were estimated at
1.5  106 ton in the European Community, 2.5  106 ton in North
America and 0.5  106 ton in Japan [4]. USA has estimated at

http://dx.doi.org/10.1016/j.fuel.2016.07.092
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.
 E.R. Umeki et al. / Fuel 185 (2016) 236–242 237

2–3 billion of tires awaiting for correct disposal [5]. According to slightly higher performer and similar gas emission than standard
the Brazilian Association of Tire Industry (ANIP), about 61 million fuel diesel [17].
of tires have been placed on the market per year in Brazil. Forecasts Although the studies point out to the use of pyrolysis conden-
point out that 50% of total amount of scrap tires are probably being sate as liquid fuel in furnaces, foundries and boilers, mainly due
disposed in inappropriate sites [6]. In 2005, 35 million of new tires to its high calorific value, low-ash and low sulfur content, its use
were inserted into Brazilian market intended for domestic in internal combustion engines needs further studies. This work
consumption. is an experimental investigation to evaluate fuel properties of
Tire waste is a serious environmental problem since they serve pyrolysis oil and diesel blends. Pyrolysis oil was obtained from a
as breeding sites for mosquitoes and rodents, and feature large fire pilot scale pyrolysis of tire waste. Properties of the tire pyrolysis
hazards [5]. Tires are difficult to deteriorate, pollute various oil (TPO) were determined and related to those of conventional
ecosystems and causing damage to plant and wildlife. The disposal fuels, providing a comparative basis for actual use in motor vehi-
of scrap tires is a growing problem worldwide. In Europe, the main cles and other applications.
destinations are landfills, energy recovery, materials recycling and
export [7]. However, the growing emphasis on the recycling issue
2. Experimental methodology
has greatly influenced the management of scrap tires which gener-
ated interest in developing alternative technologies for recycling
2.1. Materials
waste. In many countries, the main destinations are still co-
processing in cement and shale and recycling industry. Neverthe-
The waste tire material was obtained by shredding of end of life
less, it is often the improper disposal of scrap tires in rivers and
tires used in drive vehicles, producing pieces with size of 2.0–
lakes (which contribute to siltation and flooding) and landfill
5.0 cm. The shredded material contains approximately 1 wt.% of
(causing great risk of fires, unfeasible compaction, and reduction
steel. The raw material was pyrolyzed in a 15 kg stainless steel
in the landfill lifetime).
reactor under N2 inert atmosphere. The pyrolysis process was car-
Traditional methods for reusing tire waste, including retreading,
ried out in batch process during 30 min at 450 °C. The product con-
incineration and grinding, have shown limitations in their applica-
tent was 43 wt.% of carbon black, 45 wt.% of liquid phase (oil) and
tions [8]. Furthermore, these residues are practically immune to
11 wt.% of non-condensed gases. Samples of diesel S10, fuel etha-
chemical and biological treatments. A substitute means for obtain-
nol and gasoline were obtained from a local gas station and they
ing unconventional fuels is the waste thermal conversion. Thus,
were also evaluated for comparison.
pyrolysis of waste tire has been identified as a promising alterna-
tive for removing scrap tires from the environment [8,9]. The pyrol-
2.2. Methods
ysis process produces a liquid phase that can be applied to power
generation in industry and as fuel in automotive engines, serving
The quantitative chemical analysis of the tire pyrolysis oil was
as unconventional fuel alternative to the petroleum derivatives.
performed by gas chromatograph coupled with an Ion Trap mass
The pyrolysis process is based on breakdown of complex mole-
spectrometry (GC/MS), using a Varian chromatograph, model
cules into simpler molecules by use of heat. It is a redox process in
Saturn 2100D (Varian, USA). It was used a HP-5MS capillary col-
which a part of the material is reduced to carbon and the other part
umn (30 m  0.25 mm  0.25 lm), containing 5% biphenyl and
is oxidized and hydrolyzed to produce a mixture of compounds,
95% di-methyl polysilane. Helium (99.9999%) was used as carrier
such as phenols, carbohydrates, alcohols, aldehydes, ketones and
gas at 1.0 mL min1. Injector was operated in split mode (1:20
carboxylic acids [2]. Pyrolysis involves heating the feedstock at
ratio) at 240 °C.
temperatures usually above 400 °C in the absence of oxygen under
The compositional analysis and fuel property determination
an inert atmosphere, leading to the decomposition and volatiliza-
were performed by mid-infrared spectrum using a Gas Sensor Por-
tion of the various structures that compose the raw material. The
table Process Analyzer (GS-PPA-I), Model GS1000 plus VOC (PAC,
process produces gaseous, liquid (condensate) and solid fractions.
USA). The analysis evaluated multiple chemical and physical prop-
Many studies show that the characteristics of the products
erties, including quantification of olefin, aromatic and saturate
obtained from the tires pyrolysis differ by operating conditions
fractions, as well as motor octane number (MON) by ASTM
such as temperature, pressure and residence time [7,10,11]. Many
D2700 Method, research octane number (RON) by ASTM D2699
works propose the use of pyrolysis-derived oil as a substitute for
Method and anti-knock index.
conventional fuels and raw material for chemical production
Specific gravity and viscosity were simultaneously obtained in a
[4,7,10,11]. Besides the environmental and sustainability benefits,
Stabinger SVM 3000 viscometer (Anton Paar, Germany). The equip-
tire pyrolysis must contribute economically to generate cheaper
ment applies the harmonic oscillation law in a U-tube filled with
fuels, if the process is deployed on a large scale.
test sample to perform dynamic viscosity and density measure-
Obtaining pyrolysis-derived oil from the scrap tire processing
ments according to ASTM D7042. From this result, the viscometer
has been addressed in several studies [8,9,12–14]. Recently, nitro-
calculates automatically the kinematic viscosity. The vapor pres-
gen has been replaced by hydrogen, with the aim to improve the
sure was obtained using a HVP972 Herzog instrument (PAC, USA)
product quality [15]. Results of this work have shown that the
by ASTM D6378 method at temperatures between 15 and 90 °C.
pyrolysis of tire waste produces significant amounts of hydrocar-
The High Heat Value (HHV) was determined by a Basic C2000 com-
bon liquids, solids and gases. The gases are essentially composed
bustion calorimeter (IKA, Germany). Elemental composition was
of hydrogen, carbon monoxide, carbon dioxide, methane, ethane
determined using a Perkin Elmer (USA) elemental analysis model
and butadiene. The condensate oil fraction has similar physical
CHN 2400 Series II, using a thermal conductivity detector.
and chemical properties to diesel, including the emission of carbon
monoxide and hydrocarbons when ignited. Nevertheless,
pyrolysis-derived oil cannot be directly used in engines before a 3. Results and discussion
pretreatment to remove impurities. It has appointed that the
pyrolysis-derived oil can be directly used in boilers or internal 3.1. Properties of tire pyrolysis oil and conventional fuels
combustion engines after the reduction in sulfur and mixing with
the diesel [16]. Blends of pyrolysis oil have been successfully tested The organic liquid phase obtained from the waste tire pyrolysis
in a 9.9 kW indirect injection multi-cylinder engine, resulting in was a dark brown oil, termed tire pyrolysis oil (TPO), presenting an
238 E.R. Umeki et al. / Fuel 185 (2016) 236–242

intense and distasteful odor. TPO properties are listed in Table 1. 1.00
Additionally, properties for gasoline (GAS), diesel containing 0.95

Specific gravity (g.cm-3)

10 ppm of sulfur (DS10) and ethanol (ETOH) are also presented
in Table 1 for comparison. Data show TPO is denser and more vis- 0.90
cous than gasoline, diesel and ethanol fuel. Regarding specification 0.85
standards, diesel must be found in the range of 0.82–0.88 g cm3 at
0.80
20 °C. However, the TPO specific gravity is very similar to other
tire-derived oils reported by the literature [11]. The high density 0.75
found in TPO means that the amount of fuel injected into the 0.70
engine per unit volume will be increased, affecting the engine per-
0.65
formance. In addition, the emission of gases (such as carbon
monoxide and carbon dioxide) and particles will be affected. TPO 0.60
10 15 20 25 30 35 40 45 50
is substantially more viscous than other conventional fuels evalu-
Temperature (oC)
ated in this study. Literature has reported a wide range of viscosity
values for pyrolytic oils [8,11,18,19]. TPO viscosity must be a Fig. 1. Specific gravity as a function of temperature for TPO and conventional fuels:
restrictive parameter if TPO is supposed to be injected directly into j tire pyrolysis oil; N diesel S10; r ethanol fuel and d gasoline.
diesel engines [20]. The tire pyrolysis oil presents elemental com-
position and hydrogen/carbon ratio very similar to those obtained
from diesel. Table 2
Representative mathematic models for main properties of pure fuels.
Fig. 1 presents specific gravity versus temperature curves for tire
pyrolysis oil, gasoline, diesel, and ethanol fuel. Specific gravity Property Specific gravity Dynamic Vapor pressure
curves decrease smoothly linear and almost parallel with the tem- viscosity
Model q = aT + b l = aeb/T Log Pv = a/T + b
perature increasing in such way that the values obey the order:
SGTPO > SGDS10 > SGETOH > SGGAS. The linear relations between a b a b a b
specific gravity and temperature are shown in Table 2. All of TPO 0.0007 0.8546 0.0012 2463.7 1.7519 6.3318
adjusted coefficients were higher than 0.99. DS10 0.0009 0.7653 0.0031 2048.3 1.4725 5.062
GAS 0.0007 0.9457 0.0025 1872.4 1.5694 6.7996
Dynamic viscosity decreases exponentially with the tempera-
ETOH 0.0009 0.8301 0.0019 1636.1 2.2510 8.4488
ture increasing for all of the fuels, as shown in Fig. 2. The curves
in Fig. 2 show a smooth exponential decrease in viscosity with
increasing temperature for TPO, diesel and ethanol fuel. The gaso-
line curve shows a linear decaying. TPO viscosity was 5.3939 mPa s 7
Dynamic Viscosity (mPa.s)

at 20 °C and 3.1662 mPa s at 40 °C. The last value corresponds to 6

3.3998 cSt. As a contrast, Williams et al. reports the kinematic vis-
cosity value of 6.3 cSt at 40 °C in their studies on pyrolysis oil [4]. 5
Viscosity data were plotted against the temperature reciprocal and 4
an exponential mathematical model was fitted to data. Equations
for viscosity exponential models are presented in Table 2. Adjust 3
coefficients were always higher than 0.98. Viscosity is one of the
2
most important properties for engine fuels. Specifying the fuel
minimum viscosity must avoid loss of energy due to injection 1
and the injector pump leaks. Fuel viscosity should be limited to a
0
maximum value resulting from engine design, size and injection 10 15 20 25 30 35 40 45 50
characteristics of the system.
Temperature (oC)
The vapor pressure (VP) is a relative measurement of the liquid
volatility. Curves of vapor pressure for fuel investigated in this Fig. 2. Dynamic viscosity as a function of temperature for TPO and conventional
work are shown in Fig. 3. VP curves obey an exponential increasing fuels: j tire pyrolysis oil; N diesel S10; r ethanol fuel, and d gasoline.
tendency. Gasoline vapor pressure is higher than that for the others
fuels, in agreement with literature data, whereas TPO is slightly
lighter and more volatile than Diesel. Logarithmic of the vapor 350
pressure was plotted against the temperature reciprocal. Equations
of the linearized curves for vapor pressure of pure fuels are also 300
Vapor Pressure (kPa)

presented in Table 2.
250

200
Table 1
Properties of tire pyrolysis oil and conventional fuels. 150
Property TPO GAS DS10 ETOH 100
Specific gravity (g cm3) at 20 °C 0.9313 0.7479 0.8406 0.8125
Dynamic viscosity (mPa.s) à 20 °C 5.5393 0.59925 3.41998 1.55878 50
Water content (wt.%)a 0.1793 0.1533 0.0161 7.3598
Elemental analysis (wt.%)
0
C 85.71 77.09 86.23 –
-50
H 10.01 13.83 13.00 –
10 20 30 40 50 60 70 80 90 100
N 0.32 0.06 0.10 –
H/C ratio 0.12 0.18 0.15 – Temperature (oC)
a
Water content was determinate by the Karl-Fischer method, which is based on Fig. 3. Vapor pressure as a function of temperature for TPO and conventional fuels:
potentiometric titration of the sample by Karl Fischer reagent. j tire pyrolysis oil; N diesel S10; r ethanol fuel and d gasoline.
 E.R. Umeki et al. / Fuel 185 (2016) 236–242 239

Parameters of the mathematic models for pure fuel properties Table 4

as a function of temperature are summarized at Table 2. Data show Chemical composition of tire pyrolysis oil determined by GC–MS.

that specific gravity of pure fuels decreases similarly with the tem- Retention Chemical compound Chemical Normalized
perature. Dynamic viscosity and vapor pressure obey an exponen- time structure peak area
tial decay model. TPO viscosity decays fastest with the (min) (%)

temperature. Ethanol has the highest increasing rate for vapor 5.38 Toluene C7H8 4.91
pressure. 9.25 Ethyl benzene C8H10 6.32
9.72 Xylene (1) C8H10 5.96
Mid-infrared spectroscopy analysis (Mid-IR) revealed that the 10.92 Xylene (2) C8H10 3.51
tire pyrolysis oil is mostly composed of aromatic compounds prob- 12.78 Methyl ethyl benzene (cumene) C9H12 2.08
ably linked to unsaturated hydrocarbon chains. The presence of 15.37 Methyl ethyl benzene (cumene) C9H12 2.60
both polar and non-polar portions on the molecule structure must 17.37 Trimethylbenzene (1) C9H12 1.49
19.20 Trimethylbenzene (2) C9H12 2.25
impose an amphiphilic character to the system, similar to the pet-
19.41 1-Isopropyl-4-methyl-1-cyclohexene C10H18 2.46
roleum [19]. Table 3 lists that aromatic compounds are predomi- (menthene)
nantly toluene, xylene and other benzene derivatives. In addition, 19.54 1-Isopropyl-4-methyl-benzene (cymene) C10H14 10.20
the presence of ethers is proved to be substantial, mainly methyl 19.84 1-Methyl-4-methylethenylcyclohexene C10H16 37.19
tert-butyl ether (MTBE) and in a slighter amount di-isopropyl ether (limonene)
23.84 Trimethyl methylene cyclohexene C10H16 1.93
(DIPE). Mid-IR data display about 26% in volume of ethanol in gaso-
24.26 Dimethyl styrene C10H12 1.58
line, which is approximately in according to the local regulation for 31.00 Dimethyl dihydro indene C11H14 2.72
ethanol-gasoline blends. Gasoline presents high content of satu- 33.48 Cyclopentylbenzene C11H14 1.75
rate, aromatics, olefins and oxygenate compounds. Alkyl ethers 33.69 Benzothiazole C7H5NS 3.04
47.13 Methyl propenyl indene C13H14 4.74
were found in the gasoline as tert-amyl methyl ether (TAME), ethyl
52.79 Tetramethyl naphtalene C14H16 5.26
tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and methyl tert-
Total 100.00
butyl ether (MTBE). It must be noted that the percentage sum is
not 100%. It is a usual aspect occurring in Mid-IR measurements
because some compounds are complex structures containing
structural groups that belong to more than one fraction being ana- Many of the compounds present in tire derived oil have a
lyzed. These compounds are counted into two or more groups. prompt industrial application. Cumene has been widely used in
Main compounds existing in the tire pyrolysis oil were identi- the phenol production. Limonene has increasingly been used as
fied. Table 4 presents the main compounds identified in the tire biodegradable solvent, besides as odorizing and aromatizing com-
pyrolysis oil by gas chromatograph coupled to mass spectroscopy pound in the pharmaceutical and food industry. Alkyl-benzenes
(GC–MS). Since some compounds cannot be identified by GC–MS, and naphthalene derivatives are common industrial precursors.
the normalized chromatographic area for each component has Another important aspect is the feasible conversion of the high
been presented as a relative representation of the substance quan- hydrocarbon from TDO into minor compounds to produce a multi-
tity. Classes of compounds were displayed on occasion to represent component mixture analogue to conventional fuels.
a wide group of substances, instead of individual compounds. Table 5 summarizes the analysis of fuel properties for conven-
Results show high content of aromatic compounds, in agreement tional and tire derived fuels. Fuel analysis obtained data for Motor
with the Mid-IR data. TPO is composed essentially of hydrocarbons Octane Number (MON), Research Octane Number (RON), anti-
containing 7–14 carbon atoms on the chemical structure. Aromat- knock index (AKI) and high heat value (HHV). MON, RON and AKI
ics from TPO are compounds formed mainly by single ring alkyl- are the main methods to assess the octane number of fuels and
benzenes and polycyclic aromatics, such as indene and naph- they constitute the most important properties for fuel application
thalene derivatives. Limonene (1-methyl-4-prop-1-en-2-yl-cyclo in Otto cycle engines. RON is the most useful octane rating and it
hexene), a natural terpene, has the largest percentage of the pyrol- is obtained under variable compression rate and low speed,
ysis oil. Cymene (1-methyl-4-(1-methylethyl) benzene), an aro- whereas MON is obtained under full load engine at high speed.
matic terpene, has the second larger amount in the oil. Similar High heat value for the tire derived fuel was found to be very
composition was found in a bio-oil produced by pyrolysis from similar to that obtained from diesel, reaching 42 kJ g1. This value
palm kernel shell in a fluidized bed reactor [21]. is substantially higher than HHV from gasoline (39 kJ g1) and even
more from ethanol fuel (27 kJ g1). Since the high heat value repre-
sents the amount of energy produced by combustions of the mate-
rial, large amount of heat must be recovered from the TPO burning.
Similar HHV values for oils obtained from tire pyrolysis have been
Table 3
reported in the literature [11,22].
Identification of compound classes given in volumetric percentage in the tire
pyrolysis oil and diesel S10 by mid-infrared spectroscopy analysis. Although applying vapor pressure versus temperature data to
determine heat of vaporization can be mentioned as inaccurate
Component TPO GC
in many instances, literature review by NIST shows that the heat
MTBE 11.8 0.3 of vaporization (HOV) for ethanol is 42.3 ± 0.4 kJ mol1 (NIST,
ETOH 0.4 26.2
2016), which is in good agreement with the value presented in
TAME 0.0 0.3
ETBE 0.0 0.9 Table 3. Also, similar procedure has been tested in the literature
MEOH 0.2 0.7
DIPE 2.7 0.8
Aromatics 60.8 18.4 Table 5
Benzene 0.81 1.16 Fuel properties for conventional and tire derived fuels.
Olefins 41.43 16.8
Saturates 0.00 35.8 Fuel HHV (kJ g1) DHvap (kJ mol1) MON RON AKI
Toluene 1.43 1.50 TPO 42 33.54 87.55 102.45 95.00
Xylene 6.70 6.00 GAS 39 30.05 79.80 90.50 85.10
Oxygena 2.98 11.06 DS10 45 28.19 n.a. n.a. n.a.
a ETOH 27 43.10 109.80 134.50 122.10
Given in mass percentage.
240 E.R. Umeki et al. / Fuel 185 (2016) 236–242

0.96 10°C
15°C
0.94
20°C
25°C

Specific gravity (g.cm-3)

0.92
30°C
0.90 35°C
40°C
0.88 45°C
50°C
0.86 55°C
60°C
0.84

0.82

0.80
0 10 20 30 40 50 60 70 80 90 100
TPO Volumetric percentage (%)
Fig. 4. Specific gravity as a function of TPO composition for fuel blends at different temperatures.

10 T = 283.15 K
9 T = 288.15 K

8 T = 293.15 K
Dynamic viscosity (mPa.s)

T = 318.15 K
7
T = 323.15 K
6
T = 328.15 K
5 T = 333.15 K
4 T = 338.15 K
T = 343.15 K
3
T = 348.15 K
2
T = 353.15 K
1

0
0 10 20 30 40 50 60 70 80 90 100
TPO volumetric percentage (%)

Fig. 5. Dynamic viscosity as a function of TPO composition for fuel blends at different temperatures.

[23]. Then, the method was considered suitable to determine the
HOV for synthetic fuels. HOV from tire pyrolysis oil was found to
be higher than both gasoline and diesel HOV. MON and RON values
change strongly with the manufacturer and country, however usu-
ally RON values are in the 70–90 range and MON values are in the
80–105 range. Gasoline MON is slightly lower than the specified by
local regulatory agency (minimum 82), while the ethanol MON is
in agreement with the literature data (about 110). MON for tire
pyrolysis oil is in between the values found to gasoline and etha-
nol. Diesel cetane index (CI) was determined by the American Soci-
ety for Testing Materials (ASTM) empirical Eq. (1), which resulted
in a CI of 49.8.
CI ¼ 454:74  1641:416  D þ 774:74  D2  0:554  B
þ 97:803  ðlog BÞ
2
ð1Þ
where D represents the specific gravity at 15 °C given in g cm3 and
B represents the temperature corresponding in Celsius degree to
yield 50 vol.% of distillate.
3.2. Properties of TPO/diesel fuel blends
Mixtures of tire pyrolysis oil and diesel were prepared with dif-
ferent TPO volumetric percentages. Fuel energy content, which is
represented by the High Heat Value in Table 5, indicates the
amount of energy per mass unity that can be recovered from the
material. This becomes the specific gravity an essential property
when the subject is fuel combustion into engine. Fig. 4 presents
changes on the specific gravity of TPO/diesel blends with the vari-
ation of the TPO amount at different temperatures. Data show a
monotonic linear increase in the specific gravity of the blends with
the increase in TPO volumetric percentage, while temperature ris-
ing results in decrease in the specific gravity at each composition.
Trend for specific gravity changes with respect to the temperature
for pure fuels (Table 2) and their blends were both described by a
declining linear relationship.
Fig. 5 shows the changes in the dynamic viscosity of fuel blends
with the increase in the TPO amount in the mixture at tempera-
tures between 10 and 60 °C. On a general view, the viscosity iso-
therms present similar behavior, but their changes are more
intense at lower temperatures. Nevertheless, the blend viscosity
is always increased with the addition of TPO. Three main regions
can be stressed on the viscosity curves. Curves initially display a
substantial increase until to reach 20% of TPO, followed by a mod-
erate increase between 20 and 40%, and then viscosity grows up at
high rate from 40 vol.% of TPO. At 10 °C, viscosity changes from
4.57 mPa s (pure diesel) to 8.74 mPa s (pure TPO), which repre-
sents a variation of 4.16 mPa s. At 60 °C, the variation is only
 E.R. Umeki et al. / Fuel 185 (2016) 236–242 241

1.60
TDO-1.0
1.40 TDO-0.9
TDO-0.8
1.20
TDO-0.7
1.00 TDO-0.6
TDO-0.5
0.80
Log [Pv(kPa)]
TDO-0.4
0.60 TDO-0.3
TDO-0.2
0.40
TDO-0.1
0.20 TDO-0.0

0.00

-0.20

-0.40
2.9 3 3.1 3.2 3.3 3.4 3.5 3.6
1000/T (K-1)

Fig. 6. Logarithmic of the vapor pressure versus temperature reciprocal for fuel blends at different compositions.

30 T = 283.15 K
T = 293.15 K
25 T = 303.15 K
T = 313.15 K
Vapor pressure (kPa)

20 T = 323.15 K
T = 333.15 K
15

10

0
50 60 70 80 90 100 110
TDO volumetric percentage (%)

Fig. 7. Vapor pressure behavior as a composition function for fuel blends at different temperatures.

Table 6
Representative mathematic models for vapor pressure of TPO/diesel blends contain- their blend lines the parallelism was not observed. TPO vapor pres-
ing 60–100 vol.% of pyrolysis oil at constant temperature.
sure is higher than diesel vapor pressure. However, lines for TPO/
Model P v ap ¼ a  x3 þ b  x2 þ c  x þ d (P in kPa) diesel blends were not between the TPO and Diesel lines. Instead,
Temperature (K) a b c d R2 lines for blends were above the TDO line (except for points
between 10 °C and 30 °C for blend with 0.6% of TPO). The out-
283.15 0.0001 0.0384 3.2071 85.35 0.9918
293.15 0.0002 0.0544 4.2613 123.99 1.0000
wardly controversial result highlights the complexity related to
303.15 0.0003 0.0680 5.8242 155.96 0.9988 the chemical interactions in TPO/diesel mixtures. It may be an
313.15 0.0001 0.0335 3.2142 87.14 0.9992 indicative of the occurrence of associative phenomena, such as
323.15 0 0.0111 1.7264 50.783 0.9924 aggregation producing macromolecular structures, and further
333.15 0.0005 0.0994 6.7011 166.78 0.9577
precipitation, which may be result from the mixing process ther-
modynamic due to the reduction in solubility for some compo-
nents. Complementarily, Fig. 7 displays vapor pressure data as a
0.68 mPa s, and all of the blends have viscosity between 1.58 and function of the composition for TPO/diesel blends. The curves were
2.26 mPa s. In addition, results indicate that between 30 and plotted for TPO volumetric percentage higher than 60%. Data were
60 °C the kinematic viscosity (given by the ratio between dynamic adequately adjusted by a third degree polynomial fit, whose corre-
viscosity and specific gravity) for all of the blends obeys the local lation parameters for isothermal measurements are presented in
legislation for concern of automotive application. Table 6. For TPO concentration below 60%, vapor pressure data
Vapor pressure linearized-curves against the temperature were strongly dispersed and they show no explicit trend (see
reciprocal for different volumetric fractions of TPO are presented Fig. 8).
in Fig. 6. The linear adjusted coefficients (R2) were always higher Heat value was determined for blends in entire concentration
than 0.998. Lines for diesel and TPO were parallel, although for range. Results show a linear decrease in the HHV with the increase
242 E.R. Umeki et al. / Fuel 185 (2016) 236–242

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