Separation and Purification Technology 300 (2022) 121859

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Separation and Purification Technology

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

Effect of fractional distillation pretreatment on fuel quality of plastic waste

pyrolytic oils
Merve Sogancioglu Kalem
Environmental Engineering Department, Konya Technical University, Konya 42250, Turkey

A R T I C L E I N F O A B S T R A C T

Keywords: Today, the amount of plastic waste is increasing due to the use of more plastic. Since these wastes are composed
Fractional distillation of complex chemical compounds, when they are stored, they are difficult to degrade in the air, water and soil
Fuel environment and pose a serious environmental problem. One of the disposal methods of plastic waste is py­
Polyethylene wastes
rolysis, where valuable and useful products are obtained. The pyrolytic oil products formed in the pyrolysis
Pyrolysis
Pyrolytic oil
process can also be evaluated with their rich hydrocarbon compositions in the production of chemicals, energy
production and fuel production. However, in order to evaluate this product in various fields, it would be good to
improve the product quality with some pre-processes. In this study, the quality of HDPE and LDPE type pyrolytic
oils was improved by fractional distillation. Distillation fractions usability as fuel was examined. By measuring
the quality parameters of the bottom and distilled fraction obtained from the fraction process, its usability as
gasoline (bottoms fraction) and fuel oil (distillate fraction) were evaluated according to TS EN 2177 and TS EN
228 standards, respectively. LDPE distillation efficiencies are higher than HDPE distillation efficiencies as LDPE
pyrolytic oils are distilled more easily. The sulfur content of the distilled fractions obtained after distillation fell
below limit values and showed a positive situation in terms of the use of distilled products as gasoline. HDPE300,
HDPE400, HDPE500 and HDPE600 distillate fractions provided the standard / limit values given in TS EN 228
standards in terms of all parameters considered in the study. Similarly, in terms of all quality parameters
considered, HDPE300, HDPE400 and LDPE500, LDPE600 and LDPE700 bottom fractions are compatible with the
standard / limit values given in TS 2177 standards.

1. Introduction wastes can be recycled only 2 or 3 times by mechanical recycling

Plastic wastes must be disposed of or recycled for reasons such as the
long disintegration of plastics in nature, limited oil reserves and the
plastics obtained from petrol constrain the petrol reserves. Conventional
disposal methods are most often focused on landfill and incineration,
which contributes to important environmental problems [1,2]. In 2018
year, 8.3 billion metric tons plastic has been produced. Of that plastic
material 6.3 billion metric tons has become plastic waste and of that
wastes, only nine percent has been recycled. The vast majority (79%) is
accumulating in landfills or sloughing off in the natural environment as
litter [3].
The burning of plastic wastes causes the spreading of many corti­
cogenic compounds such as Polychlorinated Biphenyls (PCBs) into the
atmosphere and consequently causes serious problems on human health
and ecological balance [4]. Mechanical recycling and thermal recy­
cling/disposal methods play an important role in waste management.
Due to the deterioration of the quality of the produced raw material,
methods [5]. Mechanical recycling methods such as sorting, grinding,
washing and extrusion can recycle only 15–20% of plastic wastes [6].
Some of the most important elements of waste management is the
thermal treatment/recycling processes such as pyrolysis, gasification,
liquefaction and incineration. Among these processes, the advanced
thermo chemical treatment method, called pyrolysis, is gaining popu­
larity due to the increasing energy demand globally and the numerous
operational and environmental advantages it provides to the imbalanced
fuel market. Pyrolysis can be defined as a process in which long chain
organic materials are converted into short chain molecules by thermal
decomposition in an oxygen-free environment [7]. Pyrolyzed materials
turn into simpler structures as solid, liquid and gaseous products. The
product distribution (solid, liquid, gas) obtained as a result of the
breakdown in the pyrolysis of plastics, the yield and combinations of the
formed products differ depending on the type of plastic that is broken
down by pyrolysis, the reactor system, the presence of catalyst, tem­
perature and pressure [8-12].

E-mail address: msogancioglu@ktun.edu.tr.

https://doi.org/10.1016/j.seppur.2022.121859
Received 16 March 2022; Received in revised form 1 August 2022; Accepted 1 August 2022
Available online 11 August 2022
1383-5866/© 2022 Elsevier B.V. All rights reserved.
M. Sogancioglu Kalem
When thermoplastic group wastes are pyrolyzed, pyrolytic oils
(liquid product) consisting of valuable components are formed. These
oils usually consist of hydrocarbons with long chain molecules. Alkanes,
alkenes, cycloalkanes and aromatics are generally the most common
hydrocarbon compounds in plastic waste pyrolytic oils [13-15]. bNo­
wadays, these pyrolytic oils are analyzed by many analysis methods
such as FTIR, GC–MS, NMR. FTIR and GC–MS analyzes show that plastic
waste pyrolytic oils of type PE and PP are formed from alkane and alkene
compounds [16-18]. These compounds are also petroleum compounds.
Waste plastics contain a lot of energy as these were produced from pe­
troleum products [19]. These petroleum compounds are mostly
encountered in pyrolytic oil obtained as a result of pyrolysis of plastic
wastes. Therefore, pyrolytic oils of waste plastics are valuable for re­
covery. There are many studies on the characterization of these pyrolytic
oils. In these studies, pyrolytic oils have been shown to be recyclable and
economically valuable [4,5,15,20-22]. In the thermochemical recycling
of plastic wastes, plastic wastes are generally subjected to pyrolysis
either as a single type or with mixtures of them in certain proportions.
Some of the studies on the composition of liquid products released as a
result of pyrolysis of plastics are summarized in Table 1. As can be seen
from the table, liquid products formed as a result of pyrolysis of plastics
consist of alkane and alkene group hydrocarbons.
In another study in which pyrolysis of plastic wastes of PE, PP and PS
type was carried out, it was stated that liquid products contain a high
amount of hydrocarbon As a result of the pyrolysis of the mixture of PE,
PP plastics, it was determined that the liquid product contains naphtha
(C7-C10), gasoline (C5-C10) and light oil (C10-C20) [31].
The mixtures of PE, PP, PS and PET type plastic wastes collected from
urban wastes were pyrolyzed at 440 ◦ C and product fractions were
investigated. As a result of the pyrolysis event, liquid product efficiency
was determined as 80%, gas product efficiency as 17% and solid product
efficiency as 3%. C5-C9, C10-C13 group aromatics were found to be
more concentrated in the liquid product composition [32]. According to
the FTIR analysis conducted in a study in which the pyrolysis of LDPE,
PET and PP type plastic wastes in an inert atmosphere was determined,
LDPE and PET liquid products were paraffinic and the PET liquid
product was aromatic. In PP pyrolysis, while C3 group hydrocarbons
predominate, C1-C2, C4 and C6-C7 group hydrocarbons were the main
components in PET [33].
Fuel oil is a dark colored, less fluid petroleum product. Fuel oil,
which can be used in electrical, heat or steam systems, is preferred in all
kinds of industrial factories, facilities and buildings. It is easily pumped
and burns. It pollutes the air less than coal [34]. To evaluate the quality
of fuel oil, some quality parameters are taken into account. Limit values
of these parameters were given in various national and international
standards. Turkish Standards [35,36] and European Standards [37] can
be given as examples.
Gasoline, on the other hand, is a kind of fuel obtained by the
decomposition of organic compounds in petroleum, by catalytic or heat
degradation, and is used as a fuel in internal combustion engines and to
some extent in special stoves, and as a solvent [38]. Turkish Standards
Table 1
Pyrolytic oil components presented in the literature.
References Plastic Type Liquid/Oil Product Compound
[23] LDPE, HDPE, PP Naphthylamine, aromatic compounds
[24] LDPE, PS Alkanes, alkenes, aromatic compounds
[25] HDPE, LDPE, PET, Alkanes, alkenes, aromatic compounds
PP, PS
[26] PE, PP, PS Alcohols, aldehydes, acids, phenols
[27] PP,PS, PET, PE Alkanes, alkenes
[28] PE, PP, PS, PET Aromatic compounds, toluene, benzene,
naphthalene
[29] HDPE, LDPE, PS, PP, Aromatic compounds, aliphatics, phenols
PET
[30] PE, PP, PS Benzene, toluene, propane, ethane, methane
2
Separation and Purification Technology 300 (2022) 121859
[39] and European Standards [40] can be given as examples of standards
by which gasoline quality can be evaluated.
In order to evaluate the quality of gasoline and fuel oil according to
national and international standards, limit values of some important
parameters are taken into consideration. Sulfur is found naturally in
crude oil and is reduced to acceptable levels during refinery operations.
Sulfur in gasoline facilitates the formation of soot emissions and affects
the performance of vehicle emission control equipment. Therefore, the
sulfur content of gasoline indirectly affects the CO, HC and NOx emis­
sions [41]. At the same time, the sulfur in gasoline acts as a natural
lubricant. The excessive reduction of the sulfur content of the fuel causes
various problems in the engines when additives that increase the lu­
bricity of the fuel are not used [42]. According to TS EN 228 limits, the
sulfur content for gasoline should be at most 50 mg/kg. According to TS
EN 2177 fuel oil standard, the limit value should be 350 mg/kg for the
sulfur parameter.
The pour point temperature is the lowest temperature at which the
fuel can flow due to the precipitated paraffin crystals. In fuel oil com­
bustion engines, the pour point value should not exceed 38 ◦ C according
to TS 2177 criteria so that the filters can burn without clogging. The
flash point is the lowest temperature at which an ignition source causes
the vapors of the sample to ignite under certain conditions [43]. Ac­
cording to TS EN 2177 standards, the flash point should be at least 66 ◦ C.
The water content of fuel oil is one of the important factors affecting the
efficiency during combustion, and the high water content causes the
efficiency of injectors in combustion engines to decrease. At the same
time, high sediment causes clogging in engine filters and causes corro­
sion in engine parts. Ash refers to very small quantities of components
that do not have combustion properties similar to dissolved organome­
tallic and suspended solid particles formed in crude oil and petroleum
products. When the fuel burns, the inorganic components of the fuel
form ash as a product. This affects engine wear and some soot emissions.
Depending on the size of the ash particles, it may cause abrasions in the
fuel system and clogging in the filter and injectors. [44].
Octane number is technically a criterion used to evaluate the knock
quality of gasoline. The octane number of a fuel is a measure of its
combustion quality, and especially its ability to withstand harsh con­
ditions. The gasoline must have an octane quality suitable for the engine
to avoid deterioration of vehicle performance and engine damage.
Gasoline to be used in engines is selected according to the structure and
technology of the engine. Octane number measurements are made in
two ways as motor octane number (MON) and research octane number
(RON) [45].
With the discovery of crude oil in 1860, the world turned to an un­
sustainable energy consumption model based on petroleum-based fuels.
In the last 10 years, global energy production has increased by 150%,
which equates to approximately 13.7 billion tons of oil. In addition, 80%
of the basic energy needs in the chemical, energy and fuel sectors are
met from fossil fuels [46,47]. This causes the depletion of oil resources
and shows that future energy needs must be met from alternative energy
sources [47-49]. In a study in which HDPE, LDPE, PP and PS type wastes
were pyrolyzed with used waste oils, it was stated that the obtained
pyrolysis oils showed high quality and could be used as fuel in cement
kilns [50]. Mani et al. evaluated engine performance using waste plastic
and diesel fuel mixtures. It is stated that the waste plastic oil used in the
engine can be used instead of diesel fuel. 75% efficiency in engine power
has been obtained by using waste plastic oil [51]. Güngör et al. used PE
pyroysis oil as fuel in a CI engine. According to the results of the study, a
decrease in CO emissions and an increase in engine power were
observed [51]. In a study where HDPE plastic wastes catalyze pyrolysis
in fixed bed reactor, the pyrolysis oil obtained was enriched by Ni, Fe,
Mo, Ga, Ru and Co elements and a fuel with high aromatic hydrocarbon
content was obtained [52]. As a result of the use of pyrolysis oils ob­
tained from the pyrolysis of mixed plastic wastes as fuel in diesel en­
gines, it was observed that the pyrolysis oil obtained at low pyrolysis
temperatures showed higher efficiency by considering the effects on the
M. Sogancioglu Kalem
thermal efficiency and ignition time of the engine. In addition, it was
determined that the gas produced by combustion in the engine produces
NOx, UHC, CO2 and CO at low emission [53]. In addition, according to
the fuel quality analysis applied according to ASTM standards in py­
rolysis oils obtained at 450 ◦ C pyrolysis temperature of other PP and PS
type, HDPE and PS type pyrolysis oils have similar properties with
conventional fuel oil [54]. In the previous study of our work team, it was
determined that the energy value and hydrocarbon content of waste
HDPE and LDPE plastic pyrolysis oils are high [55]. In another study
aimed at improving the pyrolytic oil quality, the pyrolytic oil was
fractionated by fractional distillation method. It was determined that the
densities and viscosities of the distillation fractions obtained from the PE
type pyrolytic oils were lower than the raw pyrolytic oil. Distillation
fractions were similar to gasoline in terms of viscosity and density [56].
In recent years, distillation processes are preferred in order to recover
compounds such as various oxygen compounds and carboxylic acids
from products such as pyrolytic oils and bio oils obtained from ther­
mochemical processes and to separate unwanted compounds such as
water in these oils. The fractional (multi-stage) distillation process is
based on the principle of separating these compounds from the mixture,
based on the boiling points of the different compounds that make up the
structure of pyrolytic oils [57]. Since waste plastic pyrolytic oils contain
high amounts of energy, converting them into fuel can be a promising
solution. Considering the literature studies, there are generally studies
on the usability of pyrolysis liquids as fuel oil. There are no literature
studies to improve the quality of the pyrolysis liquid with different pre-
treatments and to evaluate them. Therefore, in this study, suggestions
were made for the use of different fractions of raw pyrolysis oils with
higher quality and fuel quality as fuel oil and gasoline.
In our previous study, the pyrolysis of waste plastics was carried out
in a fixed bed pyrolysis system. Pyrolysis oils were obtained from the
liquid capture containers of this system. For the liquid product (pyrolytic
oil), GC–MS, FTIR and thermal value analyzes were made, and as a result
of these characterization analyzes, it was determined that the hydro­
carbon content and energy values of pyrolytic oils were high [12]. In this
study, the quality of HDPE and LDPE type pyrolytic oils was improved
by fractional distillation. Distillation fractions usability as fuel was
examined. By measuring the quality parameters of the bottom and
distilled fraction obtained from the fraction process, its usability as
gasoline (bottoms fraction) and fuel oil (distillate fraction) were evalu­
ated according to TS EN 2177 and TS EN 228 standards, respectively.
2. Experimental
2.1. Production of pyrolytic oils
Pyrolytic oils were obtained from a study previously studied by our
work team [12]. Pyrolytic oils were obtained from pyrolysis of HDPE
and LDPE type waste plastics at 300 ◦ C, 400 ◦ C, 500 ◦ C, 600 ◦ C and
700 ◦ C at 5 ◦ C/min heating rate conditions (Fig. 1). In addition, since HC
content is an important parameter in fuel production, the HC content
Fig. 1. Pyrolytic oil, sample name and pyrolysis temperature.
3
Separation and Purification Technology 300 (2022) 121859
values of the raw pyrolytic oil samples we obtained in our previous study
were given in Table 2 [12].
2.2. Fractional distillation of pyrolytic oils
In this study, fractional distillation was performed in a laboratory-
scale fractional distillation system (Fig. 2). The distillation process
consists of the distillation flask, fraction column (vigro column), spiral
cooling column, digital thermometer, heater and other cooling con­
nections. 200 g pyrolytic oil sample was placed in the distillation flask
and the sample was started to be heated at 7 ◦ C/min heating rate with
the help of heater, and continued to be heated until the distillation
process ended (Fig. 3).
Volume measurements of the distilled fraction formed during the
distillation process were made depending on the time. A volume mea­
surement was made per minute. Simultaneously, the ambient tempera­
ture in the distillation flask was measured. At the end of the distillation
process, the fraction remaining in the distillation flask (bottoms fraction-
BF) and the fraction collected in the distillation vessel (distilled fraction-
DF) were obtained (Fig. 3). Some characterization analysis has been
done for these fractions.
2.3. Characterization of fractions
Some analyzes have been made for HDPE and LDPE type raw pyro­
lytic oils (RPO) and the bottom and distilled fractions obtained from the
distillation of these oils. Characterization parameters were given in
Table 3 together with the method standard by which the analysis is
made. Characterization parameters were evaluated according to TS EN
2177 and TS EN 228 standards.
2.3.1. Visual inspection
Within the scope of the project, appearance analysis was performed
for both bottom and distilled fraction. According to ASTM 4176 stan­
dard [58], it is stated that this analysis should be performed as visual
inspection. According to these standard, fuel oil should be homoge­
neous, no visible phase separation, no granular or fibrous material, and
clear and clear color for gasoline. Based on these standards, every
fraction obtained from the experiments was visually examined.
Table 2
Total hydrocarbon content between C10-C40 of raw HDPE and LDPE pyrolysis
pyrolytic oils (%) [12].
Plastic Type Pyrolysis Temperature, (◦ C) Hydrocarbon Content, (%)
HDPE 300 39.10
500 17.30
700 4.81
LDPE 300 32.80
500 14.70
700 5.70
M. Sogancioglu Kalem Separation and Purification Technology 300 (2022) 121859

As can be seen in Fig. 4, grading has been made according to the

determination of the prominence behind the sample of the bars given
from 1 to 5 in the bar graph and increasing in thickness.

2.3.2. Density
A graduated glass rod (hydrometer) with a density greater than the
liquid density at the end was placed in the sample and the density of the
sample was determined by reading the level of the glass rod at the
sample surface. The results have been compared with the density limit
values given for fuel oil and gasoline given in TS 2177 and TS EN 228
[35,39].

2.3.3. Viscosity
In the viscosity analysis, the viscosity of the sample was determined
by measuring the time it takes for a certain volume of liquid to flow
through the calibrated rotational viscometer by gravity. Dynamic vis­
cosity was obtained by multiplying the measured kinematic viscosity by
Fig. 2. Fractional distillation system [A: Distillation flask, B:Fraction column
the liquid density.
(vigro column), C:Spiral cooling column, D:Digital thermometer, E: Heater, F:
Mixer, G:Thermo-couple, H: Distillation vessel ].
2.3.4. Flash point
The automated Pensky-Martens closed cup tester, which is widely
used for all potentially flammable liquids, was used in the flash point
analysis. The flash point at the lowest temperature where the ignition
source of the device caused the vapor of the sample to be ignited was
measured.

2.3.5. Pour point

For pour point measurement, after the sample was placed on a cy­
lindrical sample glass, the top of the cylindrical glass was covered with a
cork. The thermometer was passed over the cork and brought into
contact with the sample. When the sample was not observed to move,
the temperature was noted and the pour point was determined by adding
3 ◦ C to this temperature.

2.3.6. Water and sediment content

Fig. 3. Bottoms fraction (A) ve distillate fraction (B). The water and sediment content of the sample was determined using
conical and 203 mm sized centrifuge tubes. At the end of centrifugation,
the residue remaining at the bottom of the tubes and the water
Table 3
remaining in the middle layer were separated and their amounts were
Analysis and analysis standards for HDPE and LDPE pyrolytic oils and distilla­
measured.
tion fractions.
Parameter Analysis Fraction 2.3.7. Ash
Standard
In the analysis performed according to TS EN ISO 6245 [59], the ash
Visual Inspection ASTM 4176 Bottoms fraction, distillate fraction content of the samples was determined in the ash furnace operated at
Density TS EN ISO Raw pyrolytic oil, bottoms fraction,
500 ◦ C.
12,185 distillate fraction
Viscosity TS1451 EN ISO Raw pyrolytic oil, bottoms fraction
3104 2.3.8. Sulfur
Flash Point TS EN ISO 2719 Raw pyrolytic oil, bottoms fraction In this analysis, UV fluorescence test method was used. According to
Pour Point TS 1233 ISO Raw pyrolytic oil, bottoms fraction the method, UV sulfur analyzer in accordance with TS EN ISO 20,846
3016
Water Content ASTM D 1796 Raw pyrolytic oil, bottoms fraction
[60] standard was used.
Ash TS EN ISO 6245 Raw pyrolytic oil, bottoms fraction
Total Residue ASTM D 1796 Raw pyrolytic oil, bottoms fraction, 2.3.9. Hydrocarbon, benzene and oxygen content
Sulfur TS EN ISO Raw pyrolytic oil, distillate fraction Hydrocarbon, benzene and oxygen content values were determined
20,846
by GC–MS method.
Hydrocarbon types ASTM D 5134 Raw pyrolytic oil, distillate fraction
Benzene ASTM D 5134 Raw pyrolytic oil, distillate fraction
Oxygen Content ASTM D 5134 Raw pyrolytic oil, distillate fraction 2.3.10. Motor octane number and research octane number
Motor Octane Number TS EN ISO 5163 Distillate fraction For the determination of the octane number of distillate fraction,
(MON) standard unleaded 95 octane gasoline was burned in a special single
Research Octane TS EN ISO 5164 Distillate fraction
Number (RON)
cylinder test motor under controlled conditions at different compression
ratios. Then, in this experiment motor, distilled fractions prepared with
a mixture of isooctane and normal heptane were also burned under
Appearance grading analysis was performed in accordance with the equal conditions. The mixing ratios were adjusted until the results ob­
ASTM 4176 standard [58]. In this analysis, the clarity of the fuel sample tained from the experimental mixture were the same as the gasoline
placed in the test tube or jar was graded by placing a standard bar graph sample. The volume percentage of isooctane in a mixture of isooctane
on the back of the sample and comparing its visual appearance with and normal heptane giving the same results as the gasoline sample is
standard visibility grading photographs (Fig. 4). defined as the octane number. This value gives the motor octane number

4
M. Sogancioglu Kalem
Fig. 4. Distillate fuel haze rating standard and distillate fuel chart (ASTM 4176).
(MON) of the knock measurement when the motor is not loaded and
running at low speeds, and the research octane number (RON) of the
knock measurement when the engine is under load when the engine is
forced.
3. Results and discussion
3.1. Distillation of pyrolytic oils
The fractional distillation graphs obtained as a result of the distil­
lation of pyrolytic oil obtained from pyrolysis of HDPE type waste
plastics at 5 different temperatures were given in Fig. 5 and Fig. 6. Ac­
cording to Fig. 5, it was observed that the distillation of HDPE300 py­
rolytic oil was completed within 49 min and at the end of this period,
100 mL of 200 mL pyrolytic oil was distilled into light oil (distilled oil). It
was determined that sample distillation had ended after the ambient
temperature reached 402 ◦ C for HDPE300. Also, looking at Fig. 6, the
Fig. 5. Time-dependent change of cumulative volume in the distillation process for HDPE oils.
5
Separation and Purification Technology 300 (2022) 121859
distillation rate continued at a constant speed up to 350 ◦ C and it was
found that it decreased after this temperature value. Similarly, accord­
ing to Fig. 6, it was observed that the amount of less distilled fraction
decreased after 40 min for HDPE300. In distillation of HDPE500 pyro­
lytic oil, depending on the temperature and time, the added volume
increase showed a linear increase similar to HDPE300 and HDPE400
oils. The rate of distillation started to decrease after 308 ◦ C, and the
amount of light oil (distilled product) was obtained in smaller amounts
after this temperature (Fig. 5-Fig. 6). While the distillation rate
continued with a constant speed up to 30 min, the volume of the distilled
fraction decreased from that moment on. In HDPE500 pyrolytic oil
distillation, distillation started to slow down at a lower temperature
compared to HDPE300 and HDPE400 pyrolytic oils, and it distilled
faster than the added volume amounts graph up to this temperature. As
the HC content increases, the speed of the distillation process decreases
and the distillation ends at higher times and higher temperatures [41].
Looking at Table 2, it is known that HDPE500 pyrolytic oil has less
M. Sogancioglu Kalem
Fig. 6. Temperature-dependent change of cumulative volume in the distillation process for HDPE oils.
hydrocarbon (HC) content than HDPE300 pyrolytic oil. As the pyrolysis
temperature increased, a pyrolytic oil with decreased HC content was
formed and the distillation of the pyrolytic oil began to be completed at
lower temperatures (Fig. 5-Fig. 6). The distillation time of the HDPE600
sample took 46 min in total and ended at 401 ◦ C. Distillation rate started
to decrease after 280 ◦ C. 111.9 mL of 200 mL pyrolytic oil was distilled
(Fig. 5-Fig. 6). HDPE600 sample distilled at a more stable and constant
rate than previous pyrolytic oils. Pyrolytic oils occurring in HDPE py­
rolysis turn into liquid products with lower carbon numbers at high
pyrolysis temperature and their total HC content is lower than pyrolysis
oils obtained at low temperatures [12]. For this reason, the distillation
process was carried out at a more constant speed due to the small
amount of long chain HC compounds that HDPE600 sample has. Ac­
cording to both graphs (Fig. 5-Fig. 6), the volume of distilled product
collected (added volume) increased linearly and the distillation process
continued steadily for all oil samples. The distillation of HDPE700 py­
rolytic oil was completed within 43 min, and the distillation rate
decreased after 250 ◦ C according to the data and graphics. Considering
the attached volume-time graph, the amount of distilled volume has also
decreased due to the decreasing distillation rate after 40 min (Fig. 6).
Compared to HDPE300, HDPE400, HDPE500 and HDPE600 samples,
HDPE700 pyrolytic oil distilled faster and the distillation rate decreased
at lower temperatures (Fig. 5-Fig. 6).
The fractional distillation graphics obtained as a result of the distil­
lation of pyrolytic oils obtained from the pyrolysis of LDPE type waste
plastics were given in Fig. 7-Fig. 8. It was observed that the distillation of
Fig. 7. Time-dependent change of cumulative volume in the distillation process for LDPE.
6
Separation and Purification Technology 300 (2022) 121859
LDPE300 pyrolytic oil was completed within 55 min, and at the end of
this period, 132.5 mL of 200 mL pyrolytic oil was converted to distilled
fraction (light oil) (Fig. 7). At the end of the distillation period, the
ambient temperature was measured as 400 ◦ C (Fig. 8) for LDPE300.
After this temperature value, it was determined that the LDPE distilla­
tion ended. In addition, looking at Fig. 8, it was found that the distil­
lation rate continued constant up to 365 ◦ C and the distillation rate
decreased starting from this temperature. The addition volume formed
as a result of the distillation of LDPE400 pyrolytic oil showed a linear
increase depending on time and temperature (Fig. 7- Fig. 8). For this
sample, the distillation rate has decreased since 280 ◦ C (Fig. 7). It was
determined that the distilled volume decreased after the 30th minute. At
the end of the distillation process, it was determined that 137 mL of the
LDPE400 was converted into a light oil (distilled fraction) as distilled
(Fig. 8). In LDPE500 pyrolytic oil distillation, distillation started to slow
down at a lower temperature compared to LDPE300 and LDPE400 py­
rolytic oils and it was distilled faster than the amount of added volume
up to this temperature. As the pyrolysis temperature increased, a pyro­
lytic oil with decreasing HC content (Table 2) was formed and the
distillation of the pyrolytic oil began to be completed at lower temper­
atures (Fig. 7-Fig. 8). The distillation process of LDPE600 lasted for 43
min and completed at 400 ◦ C (Fig. 7). The distillation of LDPE700 py­
rolytic oil was completed within 43 min, and the distillation rate
decreased after 265 ◦ C according to Fig. 7. The amount of distilled
volume has decreased due to the decreasing distillation rate after 31 min
(Fig. 7). Compared to LDPE300, LDPE400, LDPE500 and LDPE600
M. Sogancioglu Kalem Separation and Purification Technology 300 (2022) 121859

Fig. 8. Temperature-dependent change of cumulative volume in the distillation process for LDPE oils.

samples, LDPE700 pyrolytic oil became faster and distillation started to was calculated by calculating the difference between the time when
slow down at lower temperatures (Fig. 7-Fig. 8). distillation started and when it ended. Mean distillation time was
When the distillation findings of LDPE pyrolytic oil were evaluated, calculated by dividing the sample volume by the total distillation time.
it was determined that the pyrolytic oil obtained at 300 ◦ C pyrolysis According to Table 4, in all plastic types, as the pyrolysis temperature
temperature, similar to HDPE type, was distilled slower than the pyro­ increases, the start of distillation generally tends to occur at higher
lytic oil obtained at 700 ◦ C. The temperatures at which the distillation temperatures. It was observed that the distillation end temperature was
rate of LDPE300, LDPE400, LDPE500, LDPE600 and LDPE700 pyrolytic in the range of 400–402 ◦ C in all samples. Since both plastic types are of
oils begin to decrease are 340 ◦ C, 280 ◦ C, 272 ◦ C, 270 ◦ C and 265 ◦ C, PE group, they exhibited similar results in terms of total distillation time
respectively. It was clearly observed that as the pyrolysis temperature of and average distillation rate.
the oils increased, the distillation rate increased and the distillation rate The conversion rates of pyrolytic oils to distilled and bottom frac­
decreased. Looking at Table 2, for LDPE type, similar to HDPE type, as tions were given in Table 5. While more than 40% of HDPE type pyro­
the pyrolysis temperature increased, pyrolytic oil with low HC content lytic oils were distilled at all temperatures, more than 50% of LDPE type
was formed and consequently the distillation rates of these samples pyrolytic oils were distilled at 300 ◦ C, 400 ◦ C and 500 ◦ C temperatures.
started to decrease at lower temperatures as the HC content decreased. The carbon bonds of LDPE type plastics produced under low pressure
When the distillation efficiencies for the LDPE type are calculated conditions are weaker than HDPE type produced under high pressure
depending on the amount of distilled product obtained, it was calculated conditions [61]. For this reason, LDPE300, LDPE400 and LDPE500 py­
as 67.5%, 68.5%, 71.5%, 74.5% and 75% for LDPE300, LDPE400, rolytic oils were distilled more easily than HDPE types. Since LDPE600
LDPE500, LDPE600 and LDPE700 pyrolytic oils, respectively. It was and LDPE700 raw pyrolytic oils were obtained under high temperature
determined that as the pyrolysis temperature increased, the yields of conditions, the weak carbon bonds of these oils were broken and they
distilled products also increased. contained complex compounds. Therefore, the conversion rates of
When HDPE and LDPE types were compared, it was observed that LDPE600 and LDPE700 oils to distilled fraction have also decreased
LDPE distillation efficiencies were higher than HDPE type, and the (Table 5).
temperatures at which the distillation rate decreased were lower. The
HC content of liquid products occurring in the pyrolysis of LDPE plastics 3.2. Characterization of distillation fractions
produced under low pressure conditions is lower. According to Table 2,
LDPE type pyrolytic oils have less HC content than HDPE type oils. 3.2.1. HDPE fractions
Consequently, the LDPE type distilled faster and showed higher distil­ Within the scope of the study, appearance analysis was performed for
lation efficiencies depending on the HC content. both the bottom and the distilled fraction. In Fig. 9, the results of the
Table 4 shows the starting and ending temperatures at which appearance analysis of the distilled products obtained from HDPE type
distillation starts and the total distillation time and average distillation pyrolytic oils were given as high resolution photographs. Since the 5
rate calculated from the experimental data. The total distillation time horizontal bars in the bar graph placed in the background of each 5
samples were observed properly, the visibility grade of all the samples
Table 4 was determined as “5′′ according to the ASTM 4176 standard [58].
Distillation parameters. Visibility analyzes were made for the bottom fraction of HDPE, and it
was determined that the appearance was dark due to its completely
Pyrolytic Distillation Distillation Total Average
Oil First Final Distillation Distillation aromatic structure, and no visibility grade was detected according to
Temperature Temperature Time (dk) Rate (mL/ ASTM standards [58]. All of the samples have the same characteristics.
(◦ C) (◦ C) dk) Density and viscosity for HDPE bottom fraction and density values
HDPE300 179 402 49 6.12 for the distilled fraction were given in Table 6. According to TS EN 228
HDPE400 172 402 45 6.66 and TS EN 2177 standards [35,39], the density value for gasoline and
HDPE500 168 402 40 7.5 fuel oil should be at most 0.775 g/cm3 and 0.998, respectively. Ac­
HDPE600 183 401 46 6.52
cording to Table 6, density values for both the bottom and the distilled
HDPE700 179 402 43 6.97
LDPE300 148 400 41 7.31 fraction are below the standard value. As the pyrolysis temperature
LDPE400 169 401 41 5.88 increased, the density value increased in the distilled fractions obtained
LDPE500 199 402 44 6.81 from the pyrolysis oils, whose aromaticity increased.
LDPE600 212 402 43 6.97 Density can be counted as an indicator of the energy content of the
LDPE700 201 401 43 6.97
fuel. Generally, high density fuel has high energy content. The specific

7
M. Sogancioglu Kalem Separation and Purification Technology 300 (2022) 121859

Table 5
Coversion ratios of HDPE and LDPE pyrolytic oils.
Plastic Type Fraction Coversion Ratio (%)

LDPE300 LDPE400 LDPE500 LDPE600 LDPE700

HDPE Distillate (%) 50 52 44 50 52

Bottom (%) 50 48 56 50 48
LDPE Distillate (%) 69 65 53 42 37
Bottom (%) 31 35 47 58 63

Fig. 9. HDPE type distilled and bottom fraction images.

Table 6
Density and viscosity values for HDPE type bottom and distilled fractions.
Fraction Density (g/cm3)

Standard Value HDPE300 HDPE400 HDPE500 HDPE600 HDPE700

Bottom 0.998 (maximum) 0.894 0.888 0.890 0.909 0.935

Distillate 0.775 (maximum) 0.768 0.766 0.768 0.774 0.780
Fraction Viscosity (mm2/s)
Standard Value HDPE300 HDPE400 HDPE500 HDPE600 HDPE700
Bottom 50 (maximum) 25 29 32 33 30

gravity of the fuel is related to the density of the fuel and is expressed as
the ratio of the weight of the fuel in the same volume to the weight of the
same volume of water. Gasoline consists of mixtures of many hydro­
carbon compounds of various densities and molecular weights, and the
total density of the fuel is a function of the fuel composition. Therefore,
density is particularly related to variables such as aromatic content,
viscosity and distillation characteristics. Generally, fuel density affects
spray time, engine power, fuel consumption, fuel/air ratio and soot
emissions. However, it has more effect on soot emissions [42,62,63].
According to Table 6, the density values of the bottom and distilled
fractions of pyrolytic oils obtained at high pyrolysis temperatures
increased. Therefore, as the pyrolysis temperature increased, bottom
and distilled fractions with high energy content were obtained. It can
also be seen from Table 2 that high density fractions have high HC
content.
Viscosity parameter should not exceed 50 mm2/s according to TS EN
2177 standard. According to Table 6, the distillation bottom fractions of
pyrolytic oils remained below 50 mm2/s for all samples. As the pyrolysis
temperature increased, the viscosity of the bottom fractions of the py­
rolysis oils, whose density increased due to the increase in the concen­
tration of complex components, also increased. Viscosity value of fuels is
important in terms of storage, engine efficiency and operating condi­
tions. It is necessary to keep the viscosity within the correct range in
order to achieve the optimum efficiency of the engine. High viscosity
causes false atomization and fuel will not burn properly [64].
The sulfur contents of the HDPE type raw pyrolytic oil, distillation
fractions of these oils are graphically shown in Fig. 10. According to
these Fig., as the pyrolysis temperature increases, the sulfur content in
the pyrolysis oil also increases due to depolymerization. The sulfur
content of the distilled fraction resulting from the distillation of these
pyrolysis oils was lower than the raw pyrolytic oil for all samples, and
the sulfur content increased for the distillate fractions as the pyrolysis
temperature increased (Fig. 10a). The sulfur content for the HDPE300
distillate fraction is 15.7 mg/kg, for the HDPE700 distillate fraction this
value is 27.1 mg/kg. As a result of distillation, the sulfur content for
HDPE300 decreased by 77% compared to the raw pyrolytic oil, while it
decreased by 79% for HDPE700 (Fig. 10a). During the production of
plastic packaging, additives with high sulfur content are used as coloring
and strength enhancer [61]. Waste plastics carry the residues of organic
materials such as detergents and foodstuffs on them after use. For this
reason, waste plastics are disposed of together with sulfur compounds
originating from external substances in the pyrolysis process. As a result,
high levels of sulfur compounds occur in the content of solid, oil and gas
products of pyrolysis.
According to TS EN 228 standards, the sulfur content for gasoline
should be at most 50 mg/kg. According to Fig. 10a, while the sulfur
content of the pyrolytic oils was above the standard value, the sulfur
content of the distilled fractions after the distillation of these oils
remained below this value for all samples. Likewise, according to TS EN
2177 fuel oil standard, the standard value is given as 350 mg/kg for the
sulfur parameter, and the bottom fraction sulfur contents given in
Fig. 10b are below this value.
According to Fig. 10b, there is a reverse situation in the bottom
fractions compared to the distilled fractions, and the bottom fraction
sulfur content for all samples is higher than the sulfur content of raw
pyrolytic oils. The boiling points of sulfur compounds are generally
higher than 350 ◦ C [65]. The preferred target distillation temperature in
the experiments was 400 ◦ C and distillation was terminated from this
temperature. In the bottom fraction, some sulphurous compounds
reached the boiling point up to 400 ◦ C, and the bottom fraction

8
M. Sogancioglu Kalem
Fig. 10. Sulfur content of HDPE distillate fraction (a) and bottom fraction (b).
contained a high amount of sulfur due to the sulphurous compounds that
have not yet turned into gas until this temperature. The sulfur content of
the bottom fraction varied between 122 mg/kg and 169 mg/kg. As the
pyrolysis temperature increases, the sulfur-containing complex com­
pounds in raw pyrolytic oils increase, so it can be said that the sulfur
concentration increases as the pyrolysis temperature increases in the
bottom fraction (Fig. 10b).
Within the scope of the study, the flash point analysis of the bottom
fractions obtained from the distillation of HDPE type pyrolytic oils is
performed and given in Fig. 11a. The flash point value of all samples
showed a result above the standard value (66 ◦ C) given according to TS
EN 2177 standard [35]. While the flash point of raw pyrolytic oils varied
between 97 and 167 ◦ C, the flash point values of the bottom fraction
increased after distillation. At the same time, the flash point values of the
bottom fraction, which is planned to be used as fuel oil, are higher than
the standard values. The flash point values of raw pyrolytic oil, on the
other hand, have a lower flash point than the bottom fraction obtained
after distillation. This situation was encountered because the volatile
compounds of the raw pyrolytic oil were also removed from the envi­
ronment with the distillation process, and the flash point in the bottom
fraction increased due to the decrease of these volatile components. In
addition, due to the increasing pyrolysis temperatures, the flash point of
raw pyrolytic oils increased. It can be said that this situation is caused by
the fact that pyrolytic oils obtained at high pyrolysis temperatures
contain less volatile matter. As a result, this situation directly affected
the flash point values of the bottom fraction.
Fig. 11b shows the pour point values of the bottom fraction obtained
from pyrolytic oils. First of all, as can be seen from Fig. 1, raw pyrolytic
9
Separation and Purification Technology 300 (2022) 121859
oil has zero pour point in completely solid form (wax) at room tem­
perature. This is true for all raw pyrolytic oils studied in the study. Ac­
cording to Fig. 11b, as the pyrolysis temperature increased, the pour
point increased in the bottom fractions in general. It can be said that the
pour point is higher as the aromatic and therefore paraffinic structure
increases in the bottom fractions with high pyrolysis temperature. Since
the pour points of all samples are below the standard value, their use in
engines burning fuel oil is suitable according to TS EN 2177 standard in
terms of pour point [35].
Table 7 shows the water content, ash and total residue values of
HDPE bottom fractions. It was observed that as the pyrolysis tempera­
ture increased, the water content of the bottom fractions of pyrolytic oils
obtained from high temperatures decreased. In the experiments con­
ducted within the scope of the previous project, it was determined that
the degree of aromaticity increased as the pyrolysis temperature
increased [12]. In this case, the water in the environment is used in the
complex compound reactions that occur. While the water content of
high temperature pyrolysis oils decreases, the water content of the
bottom fractions obtained from them will also be low. Likewise, ash and
total residue contents of high temperature pyrolytic oils increased due to
the increase of depolymerization and aromaticity as the temperature
increased. All three parameters are below the standard values given in
TS2177 [35].
The HC contents of the distilled fractions, whose usability as gasoline
will be evaluated within the scope of the study, were given as two
separate parameters, aromatics and olefins in Table 8. Looking at
Table 2, it is seen that the total HC amount of raw pyrolytic oils varies
between 5 and 40% as the pyrolysis temperature increases. When the HC
M. Sogancioglu Kalem Separation and Purification Technology 300 (2022) 121859

Fig. 11. Flash point (a) and pour point (b) values of HDPE bottom fractions.

Table 7
Water, Ash and Total Sediment Content Values of HDPE bottom fractions.
Water Content (%v/v)

Standard Value (maximum) HDPE300 HDPE400 HDPE500 HDPE600 HDPE700

1 0.27 0.23 0.22 0.24 0.20

Ash (%m/m)
Standard Value HDPE300 HDPE400 HDPE500 HDPE600 HDPE700
(maximum)
0.2 0.07 0.05 0.06 0.12 0.14
Total Sediment (%m/m)
Standard Value HDPE300 HDPE400 HDPE500 HDPE600 HDPE700
(maximum)
0.15 0.08 0.12 0.19 0.21 0.18

Table 8
Olefin, aromatic hydrocarbon, benzene and oxygenated compound contents of HDPE type distilled fraction (% by mass).
HC Grup Standard Value 300 ◦ C 400 ◦ C 500 ◦ C 600 ◦ C 700 ◦ C
(maximum)

Olefins 18 2.94 2.628 0.30 – 0.61

Aromatics 42 29.42 30.21 30.91 31.81 28.68
Benzen 1 0.04 0.03 0.03 0.09 0.09
Oxygenated Compounds 2.7 0.91 0.97 0.83 1.78 1.99

types contained in pyrolytic oils are examined, it has been determined
within the scope of the previous study that most of them consist of ar­
omatics [12]. After distillation, it was observed that the amount of ar­
omatic HC in the distilled fraction structure increased compared to raw
pyrolytic oils. Standard values of olefins and aromatics according to TS
EN 228 standards were given as 18% and 42%, respectively. All samples
are below these standards.
According to Table 8, the amount of olefin group HCs decreased as
the pyrolysis temperature increased in HDPE type distilled fractions, and
the olefin HC content, which was released as a result of the decompo­
sition of the long chain molecule structure of the raw pyrolytic oils
belonging to the PE group, decreased with the increasing pyrolysis

10
M. Sogancioglu Kalem
temperature. Depending on the distilled product, it can be thought that
these olefin structures gradually decrease. Aromatic HC with shorter
chains than olefins, on the other hand, increased for all plastic types due
to depolymerization as the pyrolysis temperature increased. The dark­
ening of the color of the distilled product depending on the pyrolysis
temperature as a result of the images made in the appearance analysis
supports this situation (Fig. 9).
Benzene and oxygenated compounds in gasoline cause the release of
polycyclic aromatic hydrocarbons (PAH) into the atmosphere as a result
of combustion. Therefore, according to TS EN 228 [39], these two pa­
rameters should not exceed 1% by mass and 2.7% by mass, respectively.
According to Table 8, oxygen compound values of all distilled fractions
remained below the standard value. The benzene content of the all
fractions showed a result above this standard value. As the pyrolysis
temperatures at which pyrolytic oils were obtained increased, the
oxygenated compound and thus benzene values in the bottom fraction
generally increased. Distilled products of HDPE type have increased
benzene and oxygen content values as the pyrolysis temperature in­
creases due to the depolymerization reactions of the raw pyrolytic oil.
Motor octane number and research octane number quality parame­
ters were analyzed for HDPE300, HDPE400 and HDPE500 distilled
fraction samples, which are considered to give the best results among
other quality parameters. The motor octane number and research octane
number analysis findings were given in Table 9. Accordingly, HDPE-type
distilled fractions showed a result below the standard value in terms of
motor octane number and research octane number.
3.2.2. LDPE fractions
In Fig. 12, the results of the appearance analysis of the distilled
products obtained from LDPE type pyrolytic oils were given. Since the 5
horizontal bars in the bar graph placed in the background of each 5
samples were observed properly, the visibility grade of all the samples
was determined as “5′′ according to the ASTM 4176 standard [58].
Visibility analyzes were made for the bottom fraction of LDPE, and it
was determined that the appearance was dark due to its completely
aromatic structure, and no visibility grade was detected according to
ASTM standards [58]. All of the samples have the same characteristics.
The density and viscosity values for the bottom and distilled fractions
obtained from the distillation process of LDPE type pyrolytic oils were
given in Table 10. Accordingly, density values for both the bottom and
the distilled fraction are below the standard value. According to
Table 10, the distillation bottom fractions of pyrolytic oils remained
below 50 mm2/s for all samples. The density and viscosity values of all
bottom fractions considered to be used as fuel oil were below the stan­
dard value and showed compliance. Although the LDPE600 and
LDPE700 fractions remained below the standard value in the distilled
fraction, which is considered to be used as gasoline, other samples did
not show a result much above the standard value. In general, HDPE and
LDPE type distillate and bottom fractions showed very close results in
terms of density and viscosity values. Since LDPE plastics are PE groups
and similar decomposition reactions occur during the distillation phase
will cause similar results on the composition of the products and the
amounts of these compositions, the density and consequently the vis­
cosity values have also shown very similar results.
During the production of LDPE type plastic packages and bags,
sulfur-containing dyes are used for pulp additive or for printing on the
Table 9
Motor octane number and research octane number values of distilled fractions.
Parameter Standard HDPE300 HDPE400 HDPE500
Value
Motor Octane Number 85 73 73 77
(MON) (minumum)
Research Octane 95 81 82 82
Number (RON) (minumum)
11
Separation and Purification Technology 300 (2022) 121859
package. For this reason, waste LDPE plastics are disposed of together
with sulfur compounds originating from external substances in the py­
rolysis process. As a result, high levels of sulfur compounds occur in the
content of solid, oil and gas products. The sulfur contents of the LDPE
type pyrolytic oil and distillation fractions of these oils are graphically
given in Fig. 13. Accordingly, as the pyrolysis temperature increases, the
sulfur content within the pyrolysis oil also increases due to depoly­
merization. The sulfur content for the LDPE300 distillate fraction is 7.5
mg/kg, for the LDPE700 distillate fraction this value is 18.2 mg/kg. In
the distillate fraction formed as a result of the distillation of these py­
rolysis oils, the sulfur content was lower for all samples than the raw
pyrolytic oil, and the sulfur content increased for the distilled fractions
as the pyrolysis temperature increased. As a result of the distillation, the
sulfur content for LDPE300 decreased by 48.4% compared to the raw
pyrolytic oil, while it decreased by 71.5% for LDPE700 (Fig. 13a). Ac­
cording to Fig. 13b, bottom fraction sulfur content for all samples in
bottom fractions is higher than the sulfur content of raw pyrolytic oils.
The sulfur ratio of the bottom fraction varied between 87 mg/kg and
133 mg/kg. As the pyrolysis temperature increased, the sulfur-
containing complex compounds in raw pyrolytic oils increased, and
accordingly, as the pyrolysis temperature increased in the bottom frac­
tion, the sulfur concentration increased. According to Fig. 13b, while the
sulfur content of raw pyrolytic oils was above the standard value, the
sulfur content of the distilled fractions after the distillation of these oils
remained below this value for all samples. HDPE type plastic wastes are
generally packaging wastes containing high amounts of sulfur. LDPE
type plastic wastes are bags colored with a dye containing very little
sulfur. Therefore, the sulfur content of HDPE type plastic wastes is
higher than LDPE type plastic wastes [66]. For these reasons, according
to Fig. 10 and Fig. 13, HDPE type pyrolytic oils and distilled and bottom
fractions obtained from these oils have higher amounts of sulfur than
LDPE type pyrolytic oils and their fractions.
The flash point value of the bottom fractions obtained from the
distillation of LDPE type pyrolytic oils is above the standard value
(66 ◦ C) given in the TS EN 2177 standard [35] (Fig. 14a). While the flash
point of raw pyrolytic oils varied between 83 and 122 ◦ C, the flash point
of the bottom fraction increased after distillation. The flash point values
of the bottom fractions are above the standard values. Fuels with high
flash points are less volatile, while fuels with low flash points are more
known as volatile [63]. The flash point of LDPE pyrolytic oils is lower
than HDPE pyrolytic oils due to their high flammability components and
high thermal value [66]. After the distillation process, the flash point of
all fractions changed between 200 and 250 ◦ C due to similar decom­
position reactions. According to Fig. 14b, as the pyrolysis temperature
increased, the pour point increased in the bottom fractions in general. It
can be said that the pour point is higher as the aromatic and therefore
paraffinic structure increases in the bottom fractions with high pyrolysis
temperature. Since the pour points of all samples are below the standard
value, their use in engines burning fuel oil is suitable according to TS EN
2177 standard in terms of pour point [35].
Table 11 shows the water content, ash and total residue values of the
LDPE bottom fractions. It was observed that as the pyrolysis temperature
increased, the water content of the bottom fractions of pyrolytic oils
obtained from high temperatures decreased. Ash and total residue
contents of LDPE pyrolytic oils increased due to the increase of depo­
lymerization and aromaticity as the temperature increased. All three
parameters are below the standard values given in TS2177 [35].
According to Tables 7–14, the water content of bottom fractions
obtained from HDPE and LDPE plastic types decreased as the pyrolysis
temperature increased. It is thought that raw pyrolytic oils obtained at
high temperatures lose their water content with the temperature. This
situation also showed that the water content of the bottom fractions
decreased in the same direction. Depending on this situation, as the
pyrolysis temperature increased with the decrease of the water content,
the total sediment amount of all bottom fractions increased. The water
content, total sediment and ash amounts for all types of plastics showed
M. Sogancioglu Kalem Separation and Purification Technology 300 (2022) 121859

Fig. 12. LDPE type distilled and bottom fraction images.

Table 10
Density and viscosity values for LDPE type bottom and distilled fractions.
Fraction Density (g/cm3)

Standard Value LDPE300 LDPE400 LDPE500 LDPE600 LDPE700

Bottom 0.998(maximum) (maximum) 0.978 0.945 0.963 0.984 0.980

Distillate 0.775(maximum) (maximum) (maximum) 0.777 0.811 0.784 0.775 0.767
Fraction Viscosity (mm2/s)
Standard Value LDPE300 LDPE400 LDPE500 LDPE600 LDPE700
Bottom 50 (maximum) 23 29 22 35 38

Fig. 13. Sulfur content of LDPE distillate fraction (a) and bottom fraction (b).

similar results and it is well below the standard values, indicating that separate parameters, aromatics and olefins in Table 15. Looking at
the bottom fraction is a quality fuel oil in terms of these parameters. Table 2, it is seen that the total HC amount of raw pyrolytic oils varies
The HC contents of the distilled fractions, whose usability as gasoline between 5 and 40% as the pyrolysis temperature increases. When the HC
will be evaluated within the scope 8of the study, were given as two types contained in pyrolytic oils are examined, it has been determined

12
M. Sogancioglu Kalem Separation and Purification Technology 300 (2022) 121859

Fig. 14. Flash point (a) and pour point (b) values of LDPE bottom fractions.

the pyrolysis temperature increased in LDPE type distilled fractions, and

Table 11
the olefin HC content, which was released as a result of the decompo­
Water, Ash and Total Sediment Content Values of LDPE bottom fractions.
sition of the long chain molecule structure of the raw pyrolytic oils
Water Content (%v/v) belonging to the PE group, decreased with the increasing pyrolysis
Standard Value LDPE300 LDPE400 LDPE500 LDPE600 LDPE700 temperature. Depending on the distilled product, it can be thought that
(maximum) these olefin structures gradually decrease. Aromatic HC with shorter
1 0.33 0.31 0.29 0.25 0.27 chains than olefins, on the other hand, increased for all plastic types due
Ash (%m/m) to depolymerization as the pyrolysis temperature increased. The dark­
Standard Value LDPE300 LDPE400 LDPE500 LDPE600 LDPE700 ening of the color of the distilled product depending on the pyrolysis
(maximum)
temperature as a result of the images made in the appearance analysis
0.2 0.04 0.06 0.07 0.07 0.09
Total Sediment (%m/m) supports this situation (Fig. 12).
Standard Value LDPE300 LDPE400 LDPE500 LDPE600 LDPE700 According to TS EN 228 [39], benzene and oxygenated compounds
(maximum) parameters should not exceed 1% by mass and 2.7% by mass, respec­
0.15 0.05 0.09 0.09 0.17 0.11
tively. According to Table 12, oxygen compound values of all distilled
fractions remained below the standard value. The benzene content of the
within the scope of the previous study that most of them consist of ar­ all fractions showed a result above this standard value. As the pyrolysis
omatics [12]. After distillation, it was observed that the amount of ar­ temperatures at which pyrolytic oils were obtained increased, the
omatic HC in the distilled fraction structure increased compared to raw oxygenated compound and thus benzene values in the bottom fraction
pyrolytic oils. Standard values of olefins and aromatics according to TS generally increased. Distilled products of LDPE type have increased
EN 228 standards were given as 18% and 42%, respectively. All samples benzene and oxygen content values as the pyrolysis temperature in­
are below these standards. creases due to the depolymerization reactions of the raw pyrolytic oil.
According to Table 15, the amount of olefin group HCs decreased as

Table 12
Olefin and aromatic hydrocarbon contents of distilled fraction (% by mass).
HC Grup Standard Value 300 ◦ C 400 ◦ C 500 ◦ C 600 ◦ C 700 ◦ C
(maximum)

Olefins 18 1.296 1.16 0.543 0.842 0.87

Aromatics 42 21.004 22.237 28.359 22.053 27.117
Benzen 1 0.41 2,65 1.14 2.14 2.55
Oxygenated Compounds 2.7 1.23 1,45 1,96 1.41 2.37

13
M. Sogancioglu Kalem Separation and Purification Technology 300 (2022) 121859

Table 13 3.3. Evaluation of fuel analysis findings According to standards

Evaluation of distilled fractions according to standard values[✓: It provides the
standard value. ×: Does not provide standard value.]. A summary table about whether the fuel analyzes performed within
Quality HDPE300 HDPE400 HDPE500 HDPE600 HDPE700 the scope of the study meet the standard values given in the standards is
Parameter prepared and given for the distillate and bottom fractions in Table 13
Visibility ✓ ✓ ✓ ✓ ✓ and Table 14. HDPE300, HDPE400, HDPE500 and HDPE600 fractions
Density ✓ ✓ ✓ ✓ × for the distillate fractions that will be evaluated as gasoline provided the
Sulfur ✓ ✓ ✓ ✓ ✓ standard values given in the standards for all of the quality parameters
Hydrocarbon ✓ ✓ ✓ ✓ ✓
considered appropriate to be examined within the scope of the study. In
Content
Benzen ✓ ✓ ✓ ✓ ✓ terms of bottom fractions, HDPE300 and HDPE400 fuel oil provide the
Oxygenated ✓ ✓ ✓ ✓ ✓ standard values of the parameters given in the standards and considered
Compounds appropriate to be examined in this study.
Quality LDPE300 LDPE400 LDPE500 LDPE600 LDPE700
Parameter
Visibility ✓ ✓ ✓ ✓ ✓ 3.4. Statistical Evaluation of fuel analysis findings
Density × × × ✓ ✓
Sulfur ✓ ✓ ✓ ✓ ✓
Hydrocarbon ✓ ✓ ✓ ✓ ✓ In order to determine the gasoline and fuel oil properties of the
Content fractions obtained in the study (Table 15), the data of the analyzed
Benzen ✓ × × × × parameters were modeled statistically, and the optimum fractions that
Oxygenated ✓ ✓ ✓ ✓ ✓ could be considered as gasoline and fuel oil were determined. For this,
Compounds
IBM SPSS Statistics 22.0 and another version of IBM SPSS Statistics 24.0
package programs were used to verify the results. The standard values of
all quality parameters given in TS 2177 and TS EN 228 standards were
Table 14 taken as a reference in the program [35,39].
Evaluation of bottom fractions according to standard values[✓: It provides the The correlation percentage of all parameters separately according to
standard value. ×: Does not provide standard value.].
pyrolysis temperatures was determined, and ANOVA [67] was per­
Quality HDPE300 HDPE400 HDPE500 HDPE600 HDPE700 formed to see what kind of relationship the independent variables
Parameter
(quality parameters) form among themselves and the effects of this
Visibility ✓ ✓ ✓ ✓ ✓ relationship on optimum fractions.
Density ✓ ✓ ✓ ✓ ✓ First, a multiple regression model was created with categorical data
Viscosity
and standard values were adapted to the second order polynomial
✓ ✓ ✓ ✓ ✓
Sulfur ✓ ✓ ✓ ✓ ✓
Flash Point ✓ ✓ ✓ ✓ ✓ equation given in the Eq.3–1.
Pure Point ✓ ✓ ✓ ✓ ✓ ∑ ∑ ∑
Water ✓ ✓ ✓ ✓ ✓ Z = x+ Bi .Xi + Bij .Xi Xj + Bii .Xi2 (3-1)
Content
Total ✓ ✓ × × × Z: Estimated answer (for each fraction),
Sediment x: fixed response value (analysis result) at the central point,
Ash ✓ ✓ ✓ ✓ ✓ Linear coefficient βi, interactive coefficient βij and quadratic coeffi­
Quality LDPE300 LDPE400 LDPE500 LDPE600 LDPE700
cient βii.
Parameter
Visibility ✓ ✓ ✓ ✓ ✓ The formula obtained after writing the coefficients and variables in
Density ✓ ✓ ✓ ✓ ✓ their places is as follows (Eq. 3–2);
Viscosity ✓ × ✓ ✓ ✓ Z = x + (a.X1) + (b.X2) + (c.X3) + (d.X4) + (e.X5) + (f.X6) +
Sulfur ✓ ✓ ✓ ✓ ✓ (g.X7) + (h.X8) + (aa.⋅X1.⋅X2) + (ab.⋅X1.⋅X3) + (ac.⋅X1.⋅X4) + (ad.⋅X1.⋅
Flash Point ✓ ✓ ✓ ✓ ✓
Pure Point ✓ ✓ ✓ ✓ ✓
X5) + (ae.⋅X1.⋅X6) + ba.⋅(X2.⋅X3) + bb.⋅(X2.⋅X4) + bc.⋅
Water ✓ ✓ ✓ ✓ ✓ (X2.⋅X5) + bd.⋅(X2.⋅X6) + (ca.⋅X3.⋅X4) + (cb.⋅X3.⋅X5) + (cc.⋅X3.⋅X6) +
( )
Content (da.⋅X4.⋅X5) + (db.⋅X4.⋅X6) + (ea.⋅X5.⋅X6)... + hh.X82 (3-2)
Total
Definitions of variables and coefficients used in the formula are as
✓ ✓ ✓ ✓ ✓
Sediment
Ash ✓ ✓ ✓ ✓ ✓ follows.
For distilled fraction;
X1: Density (g/cm3), X2: Sulfur (mg/kg), X3: Olefins (% by mass),
X4: Aromatics (% by mass), X5: Benzene (% m/m), X6: Oxygen Content
Table 15
(%) m/m).
Parameter standard values of statistical analysis.
(a: Density Coefficient, b: Sulfur Coefficient, c: Olefins Coefficient, d:
Distilled Fraction Bottom Fraction
Aromatics Coefficient, e: Benzene Coefficient, f: Oxygen Content Coef­
Quality Parameter Standard Quality Standard ficient) (Note: The standard values were given in Table 15.).
Value Parameter Value For bottom fraction;
Density (g/cm3) <0.775 Density (g/cm3) <0.998 X1: Density (g/cm3), X2: Viscosity (mm2/s), X3: Sulfur (mg/kg), X4:
Sulfur (mg/kg) <50 Viscosity (mm2/s) <50 Flash Point (◦ C), X5: Pour Point (◦ C), X6: Water Content (% v/v), X7:
Olefins (%) Sulfur (mg/kg)
<18 <350
Sediment (% m/m), X8: Ash (% m/m).
Aromatics (%) <42 Flash Point (◦ C) greater
than66 (a: Density coefficient, b: Viscosity coefficient, c: Sulfur coefficient,
Benzen (%m/m) <1 Pure Point (◦ C) <38 d: Flash Point coefficient, e: Pour point coefficient, f: Water content
Oxygenated Compounds <2.7 Water Content (% <1 coefficient, g: Sediment coefficient; h: Ash coefficient) (Note: the stan­
(%m/m) v/v) dard values were given in Table 15.).
Total Sediment(%
Experimental design parameters used for ANOVA analysis are given
<0.15
m/m)
Ash (%m/m) <0.2 in Tables 16–17.
After writing the relevant variable values and coefficients on the
given second order polynomial model, ANOVA analysis and correlation

14
M. Sogancioglu Kalem Separation and Purification Technology 300 (2022) 121859

Table 16
Experimental design parameters used for ANOVA analysis for distilled fractions.
Quality Parameter HDPE LDPE

Mean Variance Mean of averages Mean Variance Mean of averages

Density (g/cm3) 0.77 0.20 0.80 0.78 0.25 0.79

Sulfur (mg/kg) 20.9 1.25 18.60 10.18 1.92 13.30
Olefins (%) 1.29 0.09 2.14 0.94 0.07 1.32
Aromatics (%) 30.20 2.98 24.81 24.15 3.74 19.44
Benzen (%m/m) 19.66 1.13 15.47 1.78 0.41 1.17
Oxygenated Compounds (%m/m) 1.78 0.05 1.40 1.68 0.07 1.22

Table 17
Experimental design parameters used for ANOVA analysis for distilled fractions.
Quality Parameter HDPE LDPE

Mean Variance Mean of averages Mean Variance Mean of averages

Density (g/cm3) 0.90 0.05 0.92 0.97 0.03 1.13

Viscosity (mm2/s) 29.80 2.74 25.7 29.4 3.12 32.70
Sulfur (mg/kg) 134.86 11.47 102.97 99.02 7.82 119.60
Flash Point (◦ C) 223.60 25.69 231.77 224.4 19.90 212.74
Pure Point (◦ C) 84.40 3.91 79.41 94.8 5.41 79.15
Water Content (%v/v) 0.23 0.09 0.20 0.29 0.09 0.25
Total Sediment(%m/m) 0.15 0.07 0.17 0.10 0.07 0.18
Ash (%m/m) 0.08 0.03 0.08 0.06 0.01 0.07

results according to the results of the SPSS program were given in

Table 19
Table 18 and Table 19 for distilled fractions and bottom fractions,
ANOVA analysis and correlation ratio results for bottom fractions.
respectively.
According to Table 18, the size of the correlation rates revealed Statistical HDPE300 HDPE400 HDPE500 HDPE600 HDPE700
Parameter
depending on the relationship of all quality parameters with the stan­
dard value determines the optimum distilled fraction. In general, all Sum of 154,256 154,213 158,266 152,346 157,896
Squares
samples have achieved over 70% in terms of compliance with the
Mean Squares 5963 5416 5941 5932 5842
standard values specified in the standards. Correlation rates in terms of Degrees of 26 28 27 26 27
pyrolysis temperature in all samples did not show a regular increase or a Freedom
regular decrease. Higher correlation rates were calculated for HDPE type Significance p < 0.05
than for LDPE type. According to the correlation ratio values, the Correlation %90 %92 %85 %84 %83
Ratio
distilled fraction, which gives the most appropriate analysis results with
Statistical LDPE300 LDPE400 LDPE500 LDPE600 LDPE700
the standard values specified in the standard in terms of fuel properties, Parameter
which are specified in the TS EN 228 standard [39] and considered Sum of 165,321 164,891 164,230 161,457 163,412
appropriate to be examined in this study, was the HDPE600 (Correlation Squares
rate: 93%) fraction. Mean Squares 5421 5633 5974 5632 5413
Degrees of 30 29 27 28 30
According to the ANOVA analysis and correlation ratio values given Freedom
in Table 19, when all the bottom fractions and all quality parameters are Significance p < 0.05
considered together, the standard values of the quality parameters given Correlation %94 %89 %91 %92 %92
in TS EN 2177 standards [35] and considered in this study have achieved Ratio

Table 18 a harmony between 83 and 94%. LDPE type bottom fractions gave the
ANOVA analysis and correlation ratio results for distilled fractions. highest correlation rates among species. Among all results, LDPE300
Statistical HDPE300 HDPE400 HDPE500 HDPE600 HDPE700 (Correlation rate: 94%) was the most optimum bottom fraction to be
Parameter evaluated as fuel oil in accordance with TS EN 2177 standards [35].
Sum of 156,421 162,589 153,625 167,452 165,415 In addition, since the significance value (p) is<0.05 according to the
Squares results of the ANOVA analysis, there is a significant difference be­
Mean Squares 5422 5485 4984 5412 4963 tween the groups in terms of fuel properties. This result is the same for
Degrees of 29 30 31 31 33 all fractions. Post-hoc test was applied to determine the groups caused
Freedom
by this difference and to determine the optimum pyrolysis temperature
Significance p < 0.05
Correlation %90 %92 %90 %93 %87 for distilled and bottom fractions (Tables 20–21). Tukey’s HSD (honestly
Ratio significant difference) method was preferred for this test. According to
Statistical LDPE300 LDPE400 LDPE500 LDPE600 LDPE700 the Tukey test, the optimum pyrolysis temperature was found to be
Parameter
600 ◦ C for both HDPE and LDPE types distilled fractions Table 20.
Sum of 162,534 167,841 169,880 165,549 164,122
Squares Tukey’s HSD test results of bottom fractions were given in Table 21.
Mean Squares 5123 5478 5063 5336 5463 When the significance values were examined, the optimum temperature
Degrees of 32 31 33 31 30 value for the bottom fractions was determined as 300 ◦ C.
Freedom Considering the correlation coefficients (Tables 18–19), the optimum
Significance p < 0.05
fractions of HDPE600 and LDPE300 for distilled and bottom fractions,
Correlation %80 %74 %71 %82 %83
Ratio respectively, support Tukey’s HSD results (Tables 20–21).

15
M. Sogancioglu Kalem Separation and Purification Technology 300 (2022) 121859

Table 20
Results of Tukey’s HSD test for distilled fractions.
Temperature (◦ C) Temperature (◦ C) HDPE LDPE

Mean Difference Std. Err. Significance (p) Mean Difference Std. Err. Significance (p)

300 400 0.541 0.453 0.041 0.595 0.345 0.043

500 0.247 0.453 0.077 0.272 0.345 0.081
600 0.788 0.453 0.023 0.867 0.345 0.064
700 0.146 0.453 0.071 0.161 0.345 0.055
400 300 0.676 0.453 0.044 0.744 0.345 0.016
500 0.309 0.453 0.082 0.340 0.345 0.087
600 0.985 0.453 0.025 1.084 0.345 0.026
700 0.183 0.453 0.076 0.201 0.345 0.080
500 300 0.720 0.453 0.045 0.791 0.345 0.047
400 0.329 0.453 0.085 0.361 0.345 0.039
600 1.048 0.453 0.025 1.153 0.345 0.027
700 0.194 0.453 0.078 0.214 0.345 0.082
600 300 0.606 0.453 0.007 0.667 0.345 0.005
400 0.277 0.453 0.009 0.304 0.345 0.008
500 0.883 0.453 0.003 0.971 0.345 0.007
700 0.164 0.453 0.008 0.180 0.345 0.006
700 300 0.757 0.453 0.050 0.833 0.345 0.052
400 0.346 0.453 0.093 0.380 0.345 0.098
500 1.103 0.453 0.028 1.214 0.345 0.019
600 0.204 0.453 0.086 0.225 0.345 0.090

*The mean difference is significant at the 0.05 level.

Table 21
Results of Tukey’s HSD Test for bottom fractions.
Temperature (◦ C) Temperature (◦ C) HDPE LDPE

Mean Difference Std. Err. Significance (p) Mean Difference Std. Err. Significance (p)

300 400 0.844 0.748 0.007 1.012 0.601 0.006

500 0.385 0.748 0.004 0.462 0.601 0.002
600 1.229 0.748 0.008 1.474 0.601 0.004
700 0.228 0.748 0.008 0.273 0.601 0.001
400 300 1.055 0.748 0.066 1.265 0.601 0.064
500 0.482 0.748 0.124 0.577 0.601 0.121
600 1.537 0.748 0.037 1.842 0.601 0.036
700 0.285 0.748 0.114 0.341 0.601 0.112
500 300 1.122 0.748 0.068 1.346 0.601 0.066
400 0.512 0.748 0.127 0.614 0.601 0.125
600 1.635 0.748 0.038 1.960 0.601 0.037
700 0.303 0.748 0.117 0.363 0.601 0.115
600 300 0.945 0.748 0.011 1.133 0.601 0.010
400 0.432 0.748 0.014 0.517 0.601 0.013
500 1.377 0.748 0.004 1.650 0.601 0.004
700 0.255 0.748 0.012 0.306 0.601 0.012
700 300 1.182 0.748 0.074 1.416 0.601 0.073
400 0.539 0.748 0.140 0.647 0.601 0.137
500 1.721 0.748 0.042 2.063 0.601 0.041
600 0.319 0.748 0.129 0.382 0.601 0.126

*The mean difference is significant at the 0.05 level.

4. Conclusion
In this study, pyrolytic oil samples obtained from HDPE and LDPE
type plastic wastes at various pyrolysis temperatures were divided into
two different fractions as distilled and bottom fractions by fractional
distillation method. The usability of the bottom fraction as fuel oil and
the distilled fraction as gasoline was investigated with some quality
parameters. According to the results of the study;
• Pyrolytic oils obtained at high pyrolysis temperatures for HDPE and
LDPE distilled faster than pyrolytic oils obtained at low pyrolysis
temperatures, and their distillation was completed at low ambient
temperatures. LDPE distillation efficiencies are higher than HDPE
distillation efficiencies as LDPE pyrolytic oils are distilled more
easily.
• In terms of visibility parameter, all distilled fractions are clear and
their visibility rating is 5 according to ASTM 4176 standards. All
bottom and distilled fractions comply with the limit values of TS EN
2177 and TS EN 228 standards in terms of density parameter.
• All raw pyrolytic oils have a sulfur content above the limit value
given for gasoline in terms of sulfur parameter, which is not required
to be present in high amounts in the fuel. However, the sulfur content
of the distilled fractions obtained after distillation fell below these
limit values and showed a positive situation in terms of the use of
distilled products as gasoline. Similarly, all bottom fractions ob­
tained have a sulfur content below the fuel oil standard / limit value.
All bottom and distilled fractions have lower sulfur content than raw
pyrolytic oils. Therefore, if these fractions are burned, atmospheric
gases with lower sulfur emissions will be produced.
• In terms of flash point, all of the bottom fractions showed higher
flash points than the raw pyrolytic oil samples. In addition, values
above the limit values given in the standards were obtained.
Therefore, the use of bottom fractions as fuel oil has shown a positive
situation in terms of explosion safety.

16
M. Sogancioglu Kalem
• Water content, ash and total sediment values of all bottom fractions
comply with the standards.
• HDPE300, HDPE400, HDPE500 and HDPE600 distillate fractions
provided the standard / limit values given in TS EN 228 standards in
terms of all parameters considered in the study. Similarly, in terms of
all quality parameters considered, HDPE300, HDPE400 and
LDPE500, LDPE600 and LDPE700 bottom fractions are compatible
with the standard / limit values given in TS 2177 standards.
• As a result, positive results were obtained in this study for the
evaluation of waste pyrolytic oils, which is an important environ­
mental problem. Considering the depleted oil reserves, it can be said
that alternative fuels to petrol fuels are produced. It can be said that
all bottom and distilled fractions that provide limit values in terms of
all quality parameters considered in the study can be used as fuel oil
and gasoline, respectively. However, according to the statistical
analysis studies, HDPE600 distillate fraction (correlation rate: 93%)
and LDPE600 (correlation rate: 92%) were the optimum pyrolytic
oils in the use of gasoline and fuel oil, respectively.
CRediT authorship contribution statement
Merve Sogancioglu Kalem: Conceptualization, Data curation,
Formal analysis, Funding acquisition, Investigation, Methodology,
Project administration, Resources, Software, Supervision, Validation,
Visualization, Writing – original draft, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper: [Merve Sogancioglu Kalem reports
financial support was provided by The Scientific and Technological
Research Council of Turkey (TUBITAK)].
Data availability
Data will be made available on request.
Acknowledgement
This study was financially supported by TUBITAK under grant no
118Y237.
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