energies

Article
DC Thermal Plasma Design and Utilization for the
Low Density Polyethylene to Diesel Oil
Pyrolysis Reaction
Hossam A. Gabbar 1,2, *, Mohamed Aboughaly 2 and C.A. Barry Stoute 1
1 Faculty of Energy Systems and Nuclear Science, University of Ontario Institute of Technology,
2000 Simcoe Street North, Oshawa, ON L1H 7K4, Canada; stoute.barry@gmail.com
2 Faculty of Engineering and Applied Science, University of Ontario Institute of Technology,
2000 Simcoe Street North, Oshawa, ON L1H 7K4, Canada; Mohamed.aboughaly@uoit.net
* Correspondence: Hossam.gabbar@uoit.ca

Academic Editor: Mejdi Jeguirim

Received: 25 December 2016; Accepted: 31 May 2017; Published: 7 June 2017

Abstract: The exponential increase of plastic production produces 100 million tonnes of waste plastics
annually which could be converted into hydrocarbon fuels in a thermal cracking process called
pyrolysis. In this research work, a direct current (DC) thermal plasma circuit is designed and used for
conversion of low density polyethylene (LDPE) into diesel oil in a laboratory scale pyrolysis reactor.
The experimental setup uses a 270 W DC thermal plasma at operating temperatures in the range
of 625 ◦ C to 860 ◦ C for a low density polyethylene (LDPE) pyrolysis reaction at pressure = −0.95,
temperature = 550 ◦ C with τ = 30 min at a constant heating rate of 7.8 ◦ C/min. The experimental
setup consists of a vacuum pump, closed system vessel, direct current (DC) plasma circuit, and a
k-type thermocouple placed a few millimeters from the reactant sample. The hydrocarbon products
are condensed to diesel oil and analyzed using flame ionization detector (FID) gas chromatography.
The analysis shows 87.5% diesel oil, 1,4-dichlorobenzene (Surr), benzene, ethylbenzene and traces of
toluene and xylene. The direct current (DC) thermal plasma achieves 56.9 wt. % of diesel range oil
(DRO), 37.8 wt. % gaseous products and minimal tar production. The direct current (DC) thermal
plasma shows reliability, better temperature control, and high thermal performance as well as the
ability to work for long operation periods.

Keywords: sustainable engineering; thermoplastics; pyrolysis oil; gas chromatography; diesel oil;
LDPE chemical recycling; direct current thermal plasma

1. Introduction
Nowadays plastic consumption is increasing exponentially and the annual consumption of plastics
in Europe is about 60 million tons, of which 40% are used in packing and packaging [1]. The excellent
properties of plastics have been used to replace the use of wood and metals thus increasing the annual
plastic consumption about 20 times from around 5 million tons in the 1950s to nearly 100 million
tons in 2011 [2]. It was also reported that 33 million tons of plastic waste are generated in the U.S.
based on 2013 statistics [3]. Most recycled plastics are mechanically recycled, while less than 2% is
chemically recycled [4]. Growing worldwide concerns regarding the environmental consequences of
heavy dependence on fossil fuels, particularly climate change, are likely to constrain excessive use of
fossil fuels in the near future. Thus, plastic to oil pyrolysis could have a positive environmental impact
by providing alternative fuels and reducing the carbon footprint of incineration [5]. Also, the steady
increase in energy consumption coupled with environmental pollution promotes the evolution of
alternative fuels such as plastic pyrolysis oil. Because of the increasing cost and decreasing space

Energies 2017, 10, 784; doi:10.3390/en10060784 www.mdpi.com/journal/energies

Energies 2017, 10, 784 2 of 15

of landfills, traditional methods of plastic waste recycling such as landfilling and incineration cause
irreversible environmental problems, including high NO2 and CO2 emissions [6]. In this research work
diesel range oil (DRO) in range of C10 –C28 is produced by pyrolysis of plastics and identified using a
GC-FID method applied to methanol solutions.
Thermoplastic pyrolysis is a tertiary recycling method that produces liquid hydrocarbons in an
inert thermal cracking chemical reaction [7]. The pyrolysis chemical reactions involve scission of long
chain polymers to smaller chains forming hydrocarbon products in the C4 –C40 range [8]. Polyethylene
is a major plastic component and was used as a feedstock for our experimental work. Oils produced
from plastic pyrolysis have non-acidic, sulphur-free and non-corrosive characteristics, which is a
major advantage of pyrolysis oils over fossil fuels and they can be used as feedstock in fluid catalytic
cracking (FCC) refinery units [9,10]. Pyrolysis final products are affected by reaction parameters such
as operating temperature, residence time, operating pressure, heating rate and catalysts [11].
In pyrolysis, the polymeric materials are heated to high temperatures causing the macromolecular
structures to break down into smaller molecules forming a wide range of hydrocarbons as [12,13].
Polyethylene is chosen since it is a major component of plastic waste from domestic disposal. Many
studies have been conducted on the reaction kinetics of plastic wastes to determine rates of polymer
conversion against heating rate and operating temperature [14]. As seen in Table 1, the operating
temperature is inversely proportional to residence time. Below are the first order reactions used [15]:
Pyrolysis reaction conversion
wo − wt
α= (1)
wo − w ∞
First order reaction:
dx
= k (1 − x) (2)
dt
Reaction constant:  
Ea
k = ko exp − (3)
RT
The LDPE reaction order can be assumed as n = 1 while the Ea varies with molecular weight of
sample [16]. LDPE pyrolysis activation energy is estimated at 179–188 KJ/mol [14]. LDPE pyrolysis
has less environmental impact, unlike the incineration of plastics which releases toxic and harmful
emissions such as 5.04 CO2 kg/LDPE kg [17,18]. Combustion of pyrolysis oils releases less CO2 in
comparison with LDPE incineration, with an average of 6 to 11.5% wt. % (i.e., 0.06–0.115 kg CO2 /kg
of combusted pyrolysis oil) depending on the engine load [19].
As seen below, as the operating temperature increases, the residence time decreases due to the
higher rate of thermal cracking [10]. The chosen residence time in the experimental work is 30 min
since thermal plasma has the ability to achieve a temperature higher than 500 ◦ C in that period. As seen
in Table 1, the operating temperature is inversely proportional to the residence time.

Table 1. Effect of reaction temperature on LDPE pyrolysis [18].

Reaction Temperature (◦ C) Residence Time (min), τ

440 132
450 90
460 95
470 61
500 40

In this research work, slow pyrolysis is used with a residence time of 30 min without using a
catalyst [5]. The minimum cracking temperature of LDPE is 450 ◦ C The main pyrolysis products
derived from polyethylene plastics are 1-alkenes, n-alkanes, and α,ω-dialkenes ranging from C1 to
C45+ [20]. The repetitive molecular structure of a low density polyethylene (LDPE) chain is shown in
Figure 1, below:
Energies 2017, 10, 784 3 of 15
Energies 2017, 10, 784 3 of 14
Energies 2017, 10, 784 3 of 14

Figure
Figure 1. Molecular structure
1. Molecular structure of
of aa LDPE
LDPE repetitive
repetitive unit
unit [21].
[21].
Figure 1. Molecular structure of a LDPE repetitive unit [21].
The hydrocarbon liquids liquids produced
produced werewere analyzed
analyzedby
byaaFID-GC
FID-GCmethod
methodusing
usingmethanol
methanolasasa
The [13].
asolvent
solvent hydrocarbon
[13].The
Theexpectedliquidspyrolysis
expected produced were analyzed
pyrolysisproducts
products by a in
areshown
are shown FID-GC method
in Figure
Figure using methanol
2, including
2, as a
the following
following
solvent [13]. fractions:
hydrocarbon
hydrocarbon The expected pyrolysis products are shown in Figure 2, including the following
fractions:
hydrocarbon fractions:
• Fraction 1:
Fraction 1: C66 to C10 10 hydrocarbon
hydrocarbonliquid
liquid
• Fraction
Fraction 1:
Fraction 2: C
2: C10
6 to
10 to C
to C hydrocarbon
C1616hydrocarbon
10 liquid
hydrocarbonliquid
liquid
• Fraction
Fraction 2:
3: C
C10 to
to CC 16 hydrocarbon
hydrocarbon
Fraction 3: C16 to C34 hydrocarbon liquid
16 34 liquid
liquid
 Fraction
Fraction 3:
4: C
C1634 to
to CC3450 hydrocarbon
hydrocarbon liquid
liquid
• Fraction 4: C 34 to C50 hydrocarbon liquid
 Fraction 4: C34 to C50 hydrocarbon liquid

Figure 2. Expected end-products from pyrolysis [22].

Expected end-products
Figure 2. Expected
Figure end-products from pyrolysis [22].
1.1. DC Thermal Plasma
1.1. DC
DC Thermal
Thermal Plasma
Thermal plasma technology has been under active development and is well-established in
Thermal
Thermal plasma
metallurgical plasma technology
processing technology has
has been
and material underThermal
synthesis. active development and is well-established
plasmas can achieve high temperaturesin
metallurgical
metallurgical processing
processing and material synthesis. Thermal
Thermal plasmas
plasmas can
can achieve high
through plasma torches and have the ability to decrease the reactant volume to non-leachable residue temperatures
through
[23]. Theplasma
plasma torches
torches
classification and
of and
thehave thethe
have
thermal ability to used
ability
plasma decrease theproject
to decrease
in our reactant is volume
the reactant to non-leachable
volume
low temperature to plasma residue
non-leachable
(quasi-
[23]. The[23].
residue classification
equilibrium inof the
The classification
plasma) the thermal plasma
rangeused
of the thermal
temperature of 2 ×in10
plasma our
3–3 project
used 4 K,is
×in10our aslow
project temperature
shownis low plasma plasma
temperature
in Table 2. (quasi-
equilibrium plasma)
(quasi-equilibrium in the temperature
plasma) range of
in the temperature 2 × 10
range 2 ×× 1034 –3
of3–3 K, ×as 10 4 K, as
shown inshown
Table 2.
in Table 2.
Table 2. Plasma classifications [23].
Table
Table 2. Plasma classifications [23].
Classification of Plasma Tp (K) Applications
Classification
ClassificationofofPlasma
Plasma Tp (K)
Tp (K) Applications
Applications
Hightemperature
High temperaturePlasma
Plasma (Equilibrium
(Equilibrium Plasma)
Plasma) 1086–108
106 –10 Laser
Laser fusion
fusion plasma
plasma
Low
Low temperature
High Plasma
temperature
temperature Plasma
Plasma (Quasi-equilibrium Plasma)
(Equilibrium Plasma)
(Quasi-equilibrium Plasma) 2 3×–3
2 × 10 10×
10 10×84 104
–3
63–10 Arc
Arc plasma,
Laser
plasma, atmospheric
RF RF
fusion plasma
atmospheric discharge
discharge
Non-thermal
LowNon-thermalPlasma
temperature Plasma(non-equilibrium
Plasma (non-equilibriumPlasma)
Plasma)
(Quasi-equilibrium Plasma) 300–400
2 × 300–400
10 –3 × 104
3 Corona
Arc plasma,Coronadischarge
discharge
atmospheric RF discharge
Non-thermal Plasma (non-equilibrium Plasma) 300–400 Corona discharge
Thermal plasma
Thermal plasma technology
technologycan canhelphelpdevelop
develop pyrolysis
pyrolysis reactors
reactors duedueto its
to ability to generate
its ability free
to generate
Thermal
radicals which plasma technology
accelerate chemical can help develop
reactions and pyrolysis
thermal reactors due to its ability to generate free
free radicals which accelerate chemical reactions and thermalcracking
crackingrates,
rates,causing
causing better reaction
better reaction
radicals
kinetics which accelerate
[23,24]. Plasma-assisted chemical reactions
chemical and are
reactions thermal
more cracking
energy rates, with
efficient causingless better reaction
environmental
kinetics [23,24]. Plasma-assisted chemical reactions are more energy efficient with less environmental
kinetics [23,24].
impact and
and Plasma-assisted
in addition,
addition, chemical
they increase
increase the reactions are more
process stability
stability energy efficient
and with less environmental
impact in they the process and enhance
enhance the the pyrolysis
pyrolysis chemistry
chemistry [25].
[25].
impact and
A constant in
constant heatingaddition,
heating raterate in they increase
in plastic
plastic pyrolysis the process
pyrolysis achieves stability
achieves higher and
higher oil enhance
oil yield, the pyrolysis chemistry [25].
A yield, and
and lower
lower gas gas and
and tar
tar yield
yield [26].
[26].
A constant
The thermal heating
plasma rate
can inachieve
plastic better
pyrolysis achieves
process highercontrol
chemistry oil yield,due and
to lower
its high gas and tar
energy yield [26].
density, free
The thermal plasma can achieve better process chemistry control due to its high energy density, free
The thermal
radical plasma
reactivity and can
rapidachieve better
startup and process
shutdown chemistry control
capability [27]. due to its high
Thermal plasmasenergy
can density,
also free
achieve
radical reactivity and rapid startup and shutdown capability [27]. Thermal plasmas can also achieve
radical reactivity
high thermal
thermal and rapid
efficiencies startup
of up
up toto 70%,andas
70%, shutdown
well as capability
as long
long electrode[27]. Thermal
lifetimes (upplasmas1000can
to 1000 also achieve
h) which
which in the
the
high efficiencies of as well electrode lifetimes (up to h) in
high
long thermal
term can efficiencies
justify the of
highupinitial
to 70%, as well
capital as[27].
cost long electrode lifetimes (up to 1000 h) which in the
long term can justify the high initial capital cost [27].
long term can justify
DC plasma
plasma the high
provides initialenergy
capital density
cost [27].and high temperature generation between two
DC provides aa high
high energy density and high temperature generation between two
DC
electrodes plasma
and inprovides
the presence a high
of a energy density
sufficiently high and
gas high
flow, temperature
thetheplasma generation
extends beyondbetween oftwo
oneone the
electrodes and in the presence of a sufficiently high gas flow, plasma extends beyond of
electrodes
electrodes and
in in the
the form presence
of a of a sufficiently
plasma jet. In a high gas flow, the
non-transferred arc plasma
torch, extends
the two beyond
electrodesonedoof the
not
the electrodes in the form of a plasma jet. In a non-transferred arc torch, the two electrodes do not
electrodes
participatein in the process
form of a plasma jet. In function
a non-transferred arc torch, the two theelectrodes do not
participate in the
the processand andhave havethe thesolesole function ofof
plasma
plasma generation,
generation, unlike
unlike the transferred
transferredarc
participate
torch which in the
is process
only and
suitable have
for the sole
conductive function
reactants of plasma
[24]. generation,
Using thermal unlike
plasma theintransferred
plastic arc
waste
arc torch which is only suitable for conductive reactants [24]. Using thermal plasma in plastic waste
torch which
reactions is onlybetter
achieves suitable for conductive
environmental reactants [24].
performance Using
as well as thermal
better life plasma
cycle in plastic waste
assessment and
reactions achieves better environmental performance as well as
higher process efficiency [28]. The thermal plasma also accelerates reaction kinetics and improve better life cycle assessment and
higher process efficiency [28]. The thermal plasma also accelerates reaction kinetics and improve
Energies 2017, 10, 784 4 of 15

Energies 2017, 10, 784 4 of 14

reactions achieves better environmental performance as well as better life cycle assessment and higher
process efficiency [28]. The thermal plasma also accelerates reaction kinetics and improve thermal
thermal cracking and the emission enthalpy can be adjusted easily by electric power tuning [29].
cracking and the emission enthalpy can be adjusted easily by electric power tuning [29]. Therefore,
Therefore, DC thermal plasma torches can act as a catalyst due to their excellent properties such as
DC thermal plasma torches can act as a catalyst due to their excellent properties such as high energy
high energy density, high temperature range, and high chemical reactivity [30]. Figure 3 shows a non-
density, high temperature range, and high chemical reactivity [30]. Figure 3 shows a non-transferred
transferred thermal DC plasma torch schematic diagram.
thermal DC plasma torch schematic diagram.

Figure3.3.DC
Figure DCnon-transferred
non-transferredthermal
thermalplasma
plasma[31].
[31].

Theadvantage
The advantageofofDCDCthermal
thermalplasma
plasmaisisthe theease
easeofofoperation,
operation,expected
expectedthermal
thermalefficiency
efficiencyofof90%
90%
and a possible disadvantage of small jet volume [31]. The thermal plasma used
and a possible disadvantage of small jet volume [31]. The thermal plasma used in this research work in this research work
releasesthermal
releases thermalenergy
energyasasarc
arcdischarge
discharge [24].The
[24]. TheDCDCthermal
thermalplasma
plasmaused
usedininthe
theexperiment
experimentisisa alow
low
temperaturethermal
temperature thermalplasma
plasma with
with ananinitial
initialsteep
steepramp
rampininthe
thefirst
firstminute
minutefrom 625◦ C,
from2525toto625 °C,followed
followed
bybya aconstant
constantheating
heatingrate 7.8◦ C/min.
rateofof7.8 °C/min.

1.2.
1.2.Goal
Goaland
andScope
Scope
The
Thegoal
goalofofthis
thisstudy
studywas
wastotodemonstrate
demonstratea areliable
reliableDC
DCthermal
thermalplasma
plasmasystem
systemthat
thatprovides
provides
enough
enoughthermal
thermalenergy
energy(approximately
(approximately10471047KJ/kg)
KJ/kg) for pyrolysis reactions.
reactions. The
Thepyrolysis
pyrolysisreaction
reactionis
isallowed
allowedtoto proceed
proceed forfor τ =
= 30 min andand the
the hydrocarbon
hydrocarbonproducts
productsobtained
obtainedare arecondensed
condensedusing
usinga a
cooling ◦
coolingwater condensation
water condensationsystem at 25 C.
system atThe
25 oil°C.
sample
The isoil
analyzed
sampleusing
is FID-gas
analyzedchromatography
using FID-gas
and its chemical components
chromatography are identified.
and its chemical The objective
components of the experiment
are identified. is to of
The objective assess the DC thermal
the experiment is to
plasma’s ability to work in a LDPE pyrolysis reaction system.
assess the DC thermal plasma’s ability to work in a LDPE pyrolysis reaction system.

1.3.
1.3.LDPE
LDPEDegradation
DegradationMechanism
Mechanism
The
Thedissociation
dissociationduring thermoplastic
during thermoplasticpyrolysis involves
pyrolysis free radical
involves transfer
free radical through
transfer three steps:
through three
random
steps: random scission, free radical saturation and group transfer and the rate of theseincreases
scission, free radical saturation and group transfer and the rate of these reactions reactions
under higher
increases operating
under highertemperatures. The first stepThe
operating temperatures. involves longinvolves
first step chain polymer cracking
long chain into smaller
polymer cracking
chains,
into smaller chains, including shorter chains like methane and ethane that includes free second
including shorter chains like methane and ethane that includes free radicals. The radicals.step
The
involves side involves
second step group saturation
side groupleaving free radicals
saturation in the
leaving free middle
radicals in carbons
the middleof the polymer.
carbons of theThe final
polymer.
step
Theisfinal
chain termination
step by adding an
is chain termination by R groupan
adding as R
seen below
group (Figure
as seen 4) [32]:
below (Figure 4) [32]:
Energies 2017, 10, 784 5 of 15
Energies 2017, 10, 784 5 of 14

Energies 2017, 10, 784 5 of 14

Figure4.4. LDPE
Figure LDPE degradation
degradationmechanism
mechanism[32].
[32].
Figure 4. LDPE degradation mechanism [32].
The pyrolysis
The pyrolysis reaction
reaction asas seen
seen above
above isisinitiated
initiated by
bybreaking
breaking weaker
weaker bonds
bonds producing
producing shorter
shorter
chains with
chains with free
Thefree radicals.
pyrolysis The second
reaction
radicals. The second
as step aims
seen above
step aims to have
have
is initiated
to more
bymore stable
breaking intramolecular
weaker
stable arrangements
bonds producing
intramolecular by
shorter by
arrangements
chains transfer
hydrogen with freetoradicals.
free The second
radicals, stepthe
while aims to have
third step more stableRintramolecular
involves group arrangements
addition and by of
formation
hydrogen transfer to free radicals, while the third step involves R group addition and formation of
hydrogen
smaller transfer to
hydrocarbon free radicals, while the third step involves R group addition and formation of
molecules.
smaller hydrocarbon molecules.
smaller hydrocarbon molecules.
2. Methodology
2. Methodology
2. Methodology
In order
In order to to test the
the thermal
thermal performance
performance of DC DC thermal
thermal plasma
plasma in pyrolysis
pyrolysis reactors,
reactors, Step
Step 11
In ordertestto test the thermal performance of of DC thermal plasma inin pyrolysis reactors, Step 1
involves
involves gathering
gathering reaction
reaction kinetics
kinetics and and thermal
thermal energy energy required
required by by
thermal
involves gathering reaction kinetics and thermal energy required by thermal plasma jet which thermal
plasma plasma
jet which jet which
includes
includes understanding
understanding chemical and
includes understanding chemical
physical
chemical and
and physical
properties properties of LDPE,
of LDPE, activation
physical properties activation energies
energies energies
of LDPE, activation and reaction and
and reactionreaction
constant, k.
constant,
In Step k. InDC
2, the
constant, k.Step 2, the
In thermal
Step DC thermal
plasma
2, the DC circuit
thermal plasma circuit
is designed
plasma circuit toisdesigned
is designed
achieve toto
the achieve
operating
achieve thethe operating
temperature
operating temperature
required by
temperature
required
LDPE by LDPE
required by LDPE
pyrolysis. Steppyrolysis.
pyrolysis.
3 includesStep 3 3includes
Step includes experimental
experimental experimental
work in an inert work
work inin
anan
reactor, inert
inert reactor,
reactor,
followed followed
followed
by yield by yield
by yield
calculations
calculations and
calculations andGC-FID
GC-FID analysis
analysis ofofthe
the pyrolysis
pyrolysis oil
oil collected
collected from
from
and GC-FID analysis of the pyrolysis oil collected from LDPE. In this step, the LDPE operating LDPE.
LDPE. In In
thisthis
step,step,
the the
LDPE LDPE
operating conditions
operating conditions
conditions are gathered, are gathered,
are including including
gathered, including optimum
optimum optimum cracking temperature,
cracking temperature,
cracking temperature, reaction residence
reaction residence
reaction residence time,
time, heatingtime,
heating
heating rate,rate, expected
expected product
product yield,
yield, chemical
chemical composition
composition ofofoil
oilproduced,
produced,
rate, expected product yield, chemical composition of oil produced, and dissociation or thermal energy and dissociation
and or
dissociation or
thermal
thermalper energy
energy needed per kg of LDPE. The first order reaction is derived from Equation (2) to
needed kg ofneeded
LDPE. The per first
kg of LDPE.
order The first
reaction order from
is derived reaction is derived
Equation (2) tofrom Equation
anticipate mass(2) to
loss
anticipate mass loss per unit time for the batch reactor. Step 3 involves experimental setup of main
anticipate
per mass
unit time for loss per unit
the batch time Step
reactor. for the batch reactor.
3 involves Step 3 involves
experimental experimental
setup of main equipment, setup of main
operating
equipment, operating procedure, oil products collection and FID-GC chemical analysis.
equipment,oil
procedure, operating
productsprocedure, oil products
collection and collectionanalysis.
FID-GC chemical and FID-GC chemical analysis.
3. Experimental Setup
3.
3. Experimental
Experimental Setup
Setup
The experimental setup converts LDPE into oil using a DC thermal plasma as a heating source
The
in a experimental
The experimental
pyrolysis setupatconverts
setup
reaction pressureLDPE
converts =LDPE into
−0.95 baroiloil
into using
and a DC
using a DCthermal
temperature = 550plasma
thermal plasma
°C as as
which a is
heating source
a maintained
heating in
source
ainpyrolysis reaction at pressure −0.95=bar
= equipment and temperature = 550 ◦ C which
a throughout
pyrolysis reaction
the at The
reaction. pressure −0.95
usedbar andpyrolysis
in the temperature
reactor 550 is°C
= setup ismaintained throughout
which isbelow
described maintained
in
the reaction. Thereaction.
Figure 5.the
throughout equipment Theused in the pyrolysis
equipment used inreactor setup isreactor
the pyrolysis described below
setup in Figure below
is described 5. in
Figure 5.

Figure5.5.Experimental
Figure setup.
Experimental setup.

Vacuum Pump: All other valves should be closed and V-1 opened before starting the experiment.
Vacuum Pump: All other valves should be closed and V-1 opened before starting the experiment.
Figure
The vacuum pump is used to remove 5. Experimental
air before setup.to reactor.
nitrogen supply
The vacuum pump is used to remove air before nitrogen supply to reactor.
Pure Nitrogen Gas Cylinder: All other valves should be closed and V-2 opened before allowing
Vacuum Pump: All other valves should be closed and V-1 opened before starting the experiment.
nitrogen gas to flow to the reactor at 2 bar. The vessel is filled with nitrogen till the pressure increases
The vacuum pump is used to remove air before nitrogen supply to reactor.
from −0.95 bar to 1 bar.
Energies 2017, 10, 784 6 of 14

Pure Nitrogen Gas Cylinder: All other valves should be closed and V-2 opened before allowing
nitrogen gas to flow to the reactor at 2 bar. The vessel is filled with nitrogen till the pressure increases
Energies 2017, 10, 784 6 of 15
from −0.95 bar to 1 bar.
Condensation System: The condensation system cools gaseous hydrocarbon products at a
constant rate of 35
Condensation °C/min.
System: The thermal system
The condensation plasmacools
system
gaseous is hydrocarbon
switched offproducts
before at starting
a constantthe
condensation
rate ◦
of 35 C/min.process.
The thermal plasma system is switched off before starting the condensation process.
K-Type Thermocouple:
K-Type Thermocouple: A A k-type
k-type thermocouple
thermocouple is is inserted
inserted inside
inside the
the closed
closed vessel
vessel to to get
get anan
accurate temperature profile. The thermocouple has an initial temperature of
accurate temperature profile. The thermocouple has an initial temperature of 23.5 C before starting 23.5 ◦°C before starting
the experiment.
the experiment. The The temperature
temperature profile
profileisismeasured
measuredper permin
minforfor3030min.
min.
DC Thermal Plasma: A 270 W thermal plasma probe
DC Thermal Plasma: A 270 W thermal plasma probe at the top of at the top of the
the reactor
reactor isis used
used asas the
the
heating source
heating source on on aa 15
15 gg LDPE
LDPE sample
sample and and the
the temperature
temperature profile
profile is
is recorded
recorded using
using thethe k-type
k-type
thermocouple. Both electrodes are 316 L stainless steel in a non-transferred
thermocouple. Both electrodes are 316 L stainless steel in a non-transferred thermal plasma setup thermal plasma setup
(i.e., both electrodes are inside the reactor and have a sole plasma generation function)
(i.e., both electrodes are inside the reactor and have a sole plasma generation function) in a nitrogen in a nitrogen
atmoshphere. The
atmoshphere. The direct
direct current
current thermal
thermal plasma
plasma setup
setup isis not
not cooled
cooled by by any
any cooling
cooling fluid
fluid but
but rather
rather
operates under pure nitrogen
operates under pure nitrogen gas. gas.

3.1. Operating
3.1. Operating Conditions
Conditions
In non-catalytic
In non-catalytic LDPE
LDPE pyrolysis,
pyrolysis, light
light oil
oil starts
starts toto form
form atat aa low
low reaction
reaction temperature
temperature of 430 ◦°C
of 430 C
The reaction
The reaction temperature
temperature and and reaction
reactionresidence
residencetime timeττ have
have anan impact
impact on on the
the product
product yield
yield and
and the
the
composition of
composition of the
the oil
oil produced.
produced. At 550 ◦°C,
At 550 under aa nitrogen
C, under nitrogen atmosphere,
atmosphere, polyethylene
polyethylene can can form
form
93 wt. %%oiloil
93 and 7 wt.
and % gas
7 wt. % under
gas underoptimum conditions
optimum [33]. In[33].
conditions orderIn to order
minimize undesiredundesired
to minimize products,
nitrogen gas
products, is usedgas
nitrogen andisany
usedleakandor rupture
any leakisor avoided.
ruptureWhen LDPE pyrolysis
is avoided. When LDPE is performed
pyrolysisat an
is
operating temperature
performed at an operating of 500 °C, the liquid
temperature ◦ C, the
of 500 yield obtained is 75.6
liquid yield wt. %.isThe
obtained 75.6main
wt. %.components
The main
expected of expected
components LDPE are of benzene,
LDPE are toluene,
benzene, xylene,
toluene,dimethyl-benzene,
xylene, dimethyl-benzene, trimethyl-benzene, indane,
trimethyl-benzene,
indene, methyl-indenes,
indane, naphthalene,
indene, methyl-indenes, methyl-naphthalenes,
naphthalene, ethyl-naphthalene,
methyl-naphthalenes, and other naphthalene
ethyl-naphthalene, and other
derivatives [34].
naphthalene A slow [34].
derivatives heating rate heating
A slow and longerratereaction
and longerresidence
reaction time maximizes
residence timechar production,
maximizes char
while char content
production, also increases
while char withincreases
content also higher operating
with higher temperatures
operating[35]. Oxidation [35].
temperatures and combustion
Oxidation
is avoided
and and itsisoccurrence
combustion avoided and canitsincrease
occurrencecharcan
by up to 40–55
increase charwt.by%up[35].
to Since
40–55thewt.reaction
% [35]. residence
Since the
time is longer than few seconds, a batch reactor or pressurized batch
reaction residence time is longer than few seconds, a batch reactor or pressurized batch reactorreactor is used. In the case is
of
catalyst
used. usage,
In the caseaoffluidized bed reactor
catalyst usage, is used
a fluidized bed[35]. Theisheating
reactor used [35].rateThehasheating
a direct impact
rate has a on tar
direct
production
impact on tarand the stability
production of the
and the pyrolysis
stability of theoil produced.
pyrolysis Thus, recommended
oil produced. heating rates
Thus, recommended are
heating
between
rates are between to 10 ◦ C/min.
6 to 10 6°C/min. Advantages of a batch
Advantages reactor
of a batch are are
reactor a high
a highconversion
conversionrate rate and stable
and stable
hydrocarbonproducts
hydrocarbon products [36].
[36]. Disadvantages
Disadvantages of a of
batcha batch
reactorreactor
include include to batch
batch to batch product product
variability,
variability,
high highper
labor cost labor
batchcostand
perthe
batch and theofdifficulty
difficulty large scale of production
large scale production due to theresidence
due to the extended extended
residence
time [3]. time [3].

3.2.
3.2. DC
DC Thermal
Thermal Plasma
Plasma Circuit
Circuit Design
Design
A
A non-transferred
non-transferredDC DCcircuit of of
circuit 9000 V, 30
9000 V, mA
30 mAat 60atHz
60frequency is shown
Hz frequency in Figure
is shown 6. The circuit
in Figure 6. The
consists of capacitors,
circuit consists ceramic ceramic
of capacitors, plates, diode
plates,and resistors.
diode The input
and resistors. The power
inputsource
powerofsource
the thermal
of the
plasma circuit is alternating current (AC), which is converted to direct current and the output
thermal plasma circuit is alternating current (AC), which is converted to direct current and the output impulse
power
impulseis power
270 W. is 270 W.

Figure 6.
Figure 6. DC
DC thermal
thermal plasma
plasma circuit.
circuit.
Energies 2017, 10, 784 7 of 15

Energies 2017, 10, 784 7 of 14

As shown above, C stands for capacitors, each of which has 1500 pF in two parallel loops
As shown above, C stands for capacitors, each of which has 1500 pF in two parallel loops
connected to a diode that restricts the current to pass to the capacitors which store the electric energy.
connected to a diode that restricts the current to pass to the capacitors which store the electric energy.
The thermal plasma circuit has three capacitors with 1500 pF each in series. The total circuit capacitance
The thermal plasma circuit has three capacitors with 1500 pF each in series. The total circuit
is shown below:
capacitance is shown below: 1 1
= 1 (4)
CT 1 + C12 + C13
1
= C 1
C 1 1 1 (4)
Using the above equation to calculate the total + capacitance
+ of three 1500 pF capacitors in series:
C C C
Using the above equation
1 to calculate the total
1 capacitance of three 1500 pF capacitors in series:
= 1 1 1
= 500 pF
CT =
1500pF + 1500pF + 1500pF
= 500 pF

Thus thethe
Thus total capacitance
total capacitanceininthe
thetwo
twoparallel
parallel loops is 1000
loops is 1000pFpF(i.e.,
(i.e.,11nF).
nF).Energy
Energy density
density emitted
emitted
− 7 3
byby
DCDCthermal
thermalplasma
plasmaover
overemission
emissionvolume
volume of 3.14 ×
of 3.14 10−7 m3mis calculated
× 10 is calculated below
below [37]:[37]:
1
E
Ecapacitance CV2 2CV2
= 12 =
−12 ×
× 1000
= ½ ×=1000 × 10
× 10−12 × 9000 0.04 2J = 0.04 J
2 =9000 (5) (5)
MJ/m3MJ/m3
= 0.129
= 0.129
The density of LDPE is 0.92 g/cm3 [38] so the volume of a 15 g sample is 16.3 cm3. The thermal
The density of LDPE is 0.92 g/cm3 [38] so the volume of a 15 g sample is 16.3 cm3 . The thermal
energy needed for the reaction sample is 15.705 KJ. Thus, the energy released by the 270 W DC
energy needed for the reaction sample is 15.705 KJ. Thus, the energy released by the 270 W DC thermal
thermal plasma system satisfies the energy required.
plasmaThesystem satisfies the energy required.
function of the diode is to convert the alternating current to direct current for thermal
The function
plasma generation of the diodeaishalf
creating to convert the alternating
wave rectifier as showncurrent
below into Figure
direct current
7. A halffor thermal
cycle plasma
is used to
generation
charge the capacitors, and in the response time of absence of current, the capacitors release the chargethe
creating a half wave rectifier as shown below in Figure 7. A half cycle is used to charge
capacitors, andelectrodes
load at the in the response time of
generating a absence
thermal of current,
plasma the at
torch capacitors release
the vacuum the charge
operating load atofthe
pressure
electrodes generating
−0.95 bar. a thermal plasma torch at the vacuum operating pressure of − 0.95 bar.

Figure7.7. Half
Figure Half wave
wave rectifier
rectifier simulation.
simulation.

ImaxImax
× Vmax (6)
× Vmax (6)
= 30=mA,
ImaxImax Vmax V
30 mA, = max
9000=V9000 V
Energies 2017, 10, 784 8 of 14
Energies 10, 784
2017,2017,
Energies 10, 784 8 of 815of 14

The thermalThe plasma

thermalimpulseplasma power is calculated:
impulse power is Pcalculated:
Impulse: 270 W. A K-type thermocouple
PImpulse: 270 W. A K-type thermocouple
installed fewinstalled
millimeters
few away
The thermal plasma from
millimeters the
impulse LDPE
awaypower
from sample
isthe shows
calculated:
LDPE P625.6
Impulse
sample °C as
: 270an
shows W. initial
A K-type
625.6 temperature
°C as thermocouple
an and installedand
initial temperature
a maximum fewatemperature
millimeters of 890 °C is achieved. The temperature ◦profile is presented in the Results
maximum temperature of 890 °C is achieved. The temperature profile is presenteda in
away from the LDPE sample shows 625.6 C as an initial temperature and maximum
the Results
section. Thermal plasma
temperature of can
890 ◦achieve
C is very
achieved. high
The temperatures
temperature and
profilespecial
is precautions
presented in theneed to
Results be taken
section. Thermal
section. Thermal plasma can achieve very high temperatures and special precautions need to be taken
for safetyplasma
andfor
health
can standards
safetyachieve
and health [39].
very Thetemperatures
high
standards temperature limit
and for the experiment
special
[39]. The temperature for theisexperiment
precautions
limit set toto
need 1000 °C.set
be taken
is Several
tofor safety
1000 and
°C. Several
precautions should
health be
standardstaken
[39].is a higher
The temperature
temperature limitis detected
for the using
experiment the isK-type
set to ◦ C. Several precautions
thermocouple:
1000
precautions should be taken is a higher temperature is detected using the K-type thermocouple:
should be taken is a higher temperature is detected using the K-type thermocouple:
 Switching offSwitching
the main off power supply.
the main power supply.
 Pressure test
Pressure test before on
•  Switching before
off the switching
main power the thermal
supply.
switching on theplasma thermalsystem plasmato systemprevent toleaks prevent leaks
during
• operations.
Pressure
during test before switching on the thermal plasma system to prevent leaks during operations.
operations.
 Ensure
• the pressure
 Ensure
Ensure is below
the the pressure
pressure
atmospheric
is below
is below
for optimum
atmospheric
atmospheric
plasma
for optimum
for optimum
operation.
plasmaplasma operation.
operation.

4. Experimental Results Results

4. Experimental
4. Experimental Results
As seen below,
Asaseen
As seen 270 W thermal
below, a 270
below, Wplasma
a 270 thermal operating
plasma
W thermal at aoperating
pressure
operating
plasma = −0.95
at a at
pressure bar
=−
a pressureusing
0.95 non-transferred
bar
= −0.95 using
bar non-transferred
using non-transferred
DC thermal
DCplasma
thermal
DC inplasma
thermalanplasma
inert
invacuum
an
in inert chamber
vacuum
an inert over a ceramic
chamber
vacuum chamber anozzle
overover
ceramic asnozzle
a ceramicshown asinshown
nozzle Figure in8 Figures
as shown and 9. 8 and
in Figure 9. 9.
8 and

Figure 8. DC thermal plasma emissions at vacuum pressure.

Figure
Figure 8. DC
8. DC thermal
thermal plasma
plasma emissions
emissions at vacuum
at vacuum pressure.
pressure.

Figure
Figure 9. DC 9. DC generation
generation over nozzle.
over a ceramic a ceramic nozzle.
Figure 9. DC generation over a ceramic nozzle.

The DC thermal
TheThe
DCDC plasma
thermal isplasma
thermal integrated
plasma isinside
is integrated a 1inside
integratedL pyrolysis reactor
a 1 aL 1pyrolysis
inside and
L pyrolysis tested
reactor and
reactor on a 15
tested
and gonLDPE
tested aon15a g15LDPE
g LDPE
sample. After
sample.few min
After the
few LDPE
min thesample
LDPE shrinks
sample and changes
shrinks and into molten
changes
sample. After few min the LDPE sample shrinks and changes into molten plastic, into plastic,
molten followed
plastic, by followed
followed by by
formationformation
offormation
gaseous of hydrocarbon
gaseous
of gaseous products.products.
hydrocarbon
hydrocarbon The gaseous products
TheThe
products. gaseous
gaseous areproducts
allowed
products are to condense
allowed
are allowed into
to condense
to oil intointo
condense oil oil
products.products.
In products.
FigureIn 10,Figure
DC thermal
10, DC plasma
thermal emissions
plasma on a 15
emissions g LDPE
on a 15 setup
g LDPEis
In Figure 10, DC thermal plasma emissions on a 15 g LDPE setup is shown. shown.
setup is shown.
At the end of
At the the reaction,
At the ofend
end the of thereaction,
reaction,
the gaseous
the gaseoushydrocarbon
the hydrocarbon products
products areproducts
gaseous hydrocarbon allowedto
allowed to
are escape
escape atto escape at
at atmospheric
allowed
atmospheric pressure
pressure
atmospheric through
through pressurea condensation
a condensation
through system system to form
to form
a condensation liquid
liquid
system to hydrocarbons
hydrocarbons
form liquidand and
waxeswaxes
hydrocarbons areareallowed
and to are
waxes
allowed to condense
condense as as shown
shown in in Figure
Figure 11 11
and and identified
identified using
using GC-FID.
GC-FID.
allowed to condense as shown in Figure 11 and identified using GC-FID.
 Energies 2017, 10, 784 9 of 15
Energies
Energies 2017, 2017, 10, 784
10, 784 9 of 14 9 of 14
Energies 2017, 10, 784 9 of 14

Figure 10. DC thermal plasma on a 15 g LDPE.

Figure
Figure 10. 10. DC thermal
DC thermal plasma
plasma on a 15 gon a 15 g LDPE.
LDPE.
Figure 10. DC thermal plasma on a 15 g LDPE.

Figure
Figure 11. 11.
11. Releasing
Releasing hydrocarbon
hydrocarbon
Releasing gaseous gaseous
hydrocarbon productsproducts
gaseous through through
products the condensation
the condensation
through the system. system.
Figure
Figure 11. Releasing hydrocarbon gaseous products through the condensation
condensation system.
system.

4.1. Temperature
4.1. Temperature Profile
Profile Profile
4.1. Temperature Profile
The temperature
The temperature profile
profile profile
is recorded is recorded
using using
theusing the K-type
K-type thermocouple
thermocouple for the for the DC thermal plasma.
The temperature
temperature profile isisrecorded
recorded usingthe
theK-type
K-type thermocouple
thermocouple forDCfor thermal
thethe
DCDC plasma.
thermal
thermalplasma. As
plasma.
As
As seenAs inseen
the in the
temperaturetemperature
profile, profile,
the the
initial initial temperature
temperature reading reading
is 625.6
◦ is 625.6
°C and °C and
a maximuma maximum
seenseen
in the intemperature
the temperature profile,profile,
the initial
thetemperature reading isreading
initial temperature 625.6 Cisand a maximum
625.6 °C and atemperature
maximum
temperature
temperature of 860 °C is reached. The thermal plasma showed an acceptable
gradualgradual temperature
of 860of ◦ C860
temperature °C
of is
860reached.
is reached. °C The thermal
Theisthermal
reached. plasma plasma showed
showedplasma
The thermal an acceptable
an acceptable
showed gradual temperature
an acceptable temperature
increase
gradual which is
temperature
increaseincrease
which
favored
which
is
in favored
LDPE
is favored
in LDPE
pyrolysis.
inpyrolysis.
LDPE pyrolysis.
increase which is favored in LDPE pyrolysis.
As seenAsAsin seen
Figure
seen
in 12,
Figure
in Figurethe 12,
DC the DC thermal
thermal
12, the plasma plasma
DC thermal produces
plasma
produces a high temperature
a high temperature
produces a high temperature
profile
profile on the 15
profile
on gthe 15 g
on the 15 g
thermoplastic
thermoplastic samplesamplesample
and can and can becontrolled
becan
easily easily controlled by the current
by thebycurrent toinput
inputinput the to the plasma circuit. It can
thermoplastic
thermoplastic sample and
and canbebeeasily
easilycontrolled
controlled thethe
by current
current to plasma
input the circuit.
plasma
to the It can
circuit.
plasma It can
circuit. It also
can
also be also
also
be concluded
concluded
be concluded
be concluded that the
that the
that
DC
that
DC
the
the
DC thermal
thermal plasma
DC thermal
thermal
plasma
with
plasmaplasma
with 270
with
270 W
with
270 achieve
can W can achieve
270 achieve
W can higher
W can achieve
higher temperatures
temperatures than
higher temperatures
higher temperatures
than
than
than required
requiredrequired
for for pyrolysis
pyrolysis (up (up to 860 °C).
required
for pyrolysis (up toto
for pyrolysis 860
860(up °C).
◦ C).
to 860 °C).

Figure
Figure 12. 12.
12. Temperature
Temperature profile ofprofile
Temperature of DC
DC thermal
profile DC thermal
plasma. plasma.
Figure
Figure 12. Temperature profile of
of DC thermal
thermal plasma.
plasma.
Energies 2017, 10, 784 10 of 14

4.2. Collection of Oil Samples

The hydrocarbon gaseous products from the pyrolysis experiment pass through a condensation
Energies 2017, 10, 784 10 of 15
system and the volatile oil sample is analyzed using FID gas chromatography. The oil sample
collected from
Energies a 1510,
2017, g 784
sample of LDPE and condensed oil is shown in Figure 13. 10 of 14
4.2. Collection of Oil Samples
The hydrocarbon gaseous products are condensed and the liquid products are collected using
4.2. Collection of Oil Samples
potable cooling water at 25
The hydrocarbon °C at aproducts
gaseous coolingfrom
rate the
of 35 °C/minexperiment
pyrolysis for 15 minpass
as shown
throughina Figure 15.
condensation
The hydrocarbon gaseous products from the pyrolysis experiment pass through a condensation
system and the volatile oil sample is analyzed using FID gas chromatography. The oil sample collected
system and the volatile oil sample is analyzed using FID gas chromatography. The oil sample
from a 15 g sample of LDPE and condensed oil is shown in Figure 13.
collected from a 15 g sample of LDPE and condensed oil is shown in Figure 13.
The hydrocarbon
The hydrocarbongaseous
gaseousproducts
productsare
are condensed andthe
condensed and theliquid
liquid products
products are are collected
collected usingusing
potable cooling water at 25 ◦ C at a cooling rate of 35 ◦ C/min for 15 min as shown in Figure 15.
potable cooling water at 25 °C at a cooling rate of 35 °C/min for 15 min as shown in Figure 15.

Figure 13. 7 mL of oil sample from 15 g LDPE.

Figure 13. 7 mL of oil sample from 15 g LDPE.
Figure 13. 7 mL of oil sample from 15 g LDPE.
4.3. Headspace GC-FIDGC-FID
4.3. Headspace Analysis
Analysis
4.3. Headspace GC-FID Analysis
The oil sample is analyzed
The oil sample using
is analyzed a head
using a headspace
space FID-GC with
FID-GC with methanol
methanol solution.
solution. The oil The oil sample
sample
The oil
shows sample
the is
existence analyzed
of the using
following a head space
hydrocarbon
shows the existence of the following hydrocarbon compounds: FID-GC with
compounds: methanol solution. The oil sample
shows

the1,4-dichlorobenzene,
existence of the following
C6H4Cl2
hydrocarbon compounds:
 1,4-dichlorobenzene,
 n-butyl benzene, CC6H4Cl2
10H
• 1,4-dichlorobenzene, C 6H14 Cl
4 2
 n-butyl
•  benzene,
Un-decane, C 1011H
C H
n-butyl benzene, C10 H14
14
24

 Un-decane,
• The Cfirst
Un-decane,
11H24
chromatogram
C11 H24 in Figure 14 was identified using headspace GC with an FID to
determine the C6 to C10 hydrocarbon fraction.
The The
firstfirst
chromatogram
chromatogram inin Figure
Figure14 14
waswas identified
identified using headspace
using headspace GC with anGC
FIDwith an FID to
to determine
determine the C to C hydrocarbon
the C6 to C10 hydrocarbon fraction.
6 10 fraction.

Figure 14. FID-GC from 15 g of LDPE.

Figure 14.
Figure 14.FID-GC
FID-GCfrom
from 15 gg of
ofLDPE.
LDPE.
Energies 2017, 10, 784 11 of 15

The second chromatogram was analyzed using GC-FID with methanol solvent. The labeled
retention times
Energies 2017, are for decane (C10 ), hexadecane (C16 ) and tetratriacontane (C34 ) as shown in Figure
10, 784 11 of15.
14

Figure 15.CC10
Figure15. 10, C16 and C
16 and C3434GC-FID.
GC-FID.

The
The second chromatogram
quantitative analysis ofwas
the analyzed
pyrolysis using GC-FIDinwith
oil is shown Tablemethanol solvent.
3. The data The labeled
displayed
µg
in g
retention
shows 87.9times
wt. %are for decane (C10), minor
1,4-dichlorobenzene, hexadecane (C16) of
percentages and tetratriacontane
benzene, (C34) as In
and ethylbenzene. shown
terms in
of
Figure 15. µg
hydrocarbon analysis it shows the highest concentration of 2340 g for (C10 –C16 ), followed by C16 –C34
The quantitative
and small analysis
traces of heavier C34of
–Cthe pyrolysis oil is shown in Table 3. The data displayed in shows
50 hydrocarbon content.
87.9 wt. % 1,4-dichlorobenzene, minor percentages of benzene, and ethylbenzene. In terms of
Table 3. Quantitative
hydrocarbon analysis it shows theanalysis
highestofconcentration
pyrolysis oil using a gas chromatography
of 2340 (GC).
for (C10–C16), followed by C16–C34
and small traces of heavier CCompound
34–C50 hydrocarbon content.
Result Units
1,4-Dichlorobenzene 87.9 wt.%
Table 3. Quantitative analysis of pyrolysis oil using a gas chromatography (GC).
Benzene 0.008 µg/g
Ethylbenzene
Compound Result0.041 µg/g
Units
F1 (C6 –C 10
1,4-Dichlorobenzene)-Less BTEX 87.9 61.8 µg/g
wt.%
F1 (C6 –C10 ) Including BTEX 62.4 µg/g
Benzene 0.008 µg/g
p-Xylene 0.098 µg/g
Ethylbenzene 0.041 µg/g
o-Xylene 0.183 µg/g
F1 (C6–C10)-Less
TolueneBTEX 61.80.271 µg/g
µg/g
F1 (C6–C10) Including
Total Xylenes BTEX 62.40.281 µg/g
µg/g
p-Xylene
Undecane 0.098134 µg/g
µg/g
o-Xylene
Fraction (C10 –C16 ) 0.1832340 µg/g
µg/g
Fraction (C16 –C34 )
Toluene 0.271685 µg/g
µg/g
Fraction
Total Xylenes (C34 –C50 ) 0.281<10 µg/g
µg/g
Undecane 134 µg/g
Fraction
4.4. Product Yield Results (C 10 –C 16 ) 2340 µg/g
Fraction (C16–C34) 685 µg/g
As mentioned in the Introduction, the product <10
yield from LDPE pyrolysis ◦
Fraction (C34–C50) µg/g at 550 C is 93 wt. %.
The lower hydrocarbon liquid yields can be due to higher operating temperatures which increases the
formation
4.4. ProductofYield
lightResults
hydrocarbon products such as methane and ethane. The final tar and wax sample are
weighted and considered undesired product. Below (Table 4) are the results from a 15 g LDPE sample.
As mentioned in the Introduction, the product yield from LDPE pyrolysis at 550 °C is 93 wt. %.
The lower hydrocarbon liquid yields can be due to higher operating temperatures which increases
the formation of light hydrocarbon products such as methane and ethane. The final tar and wax
sample are weighted and considered undesired product. Below (Table 4) are the results from a 15 g
LDPE sample.
Energies 2017, 10, 784 12 of 15

Table 4. Quantitative analysis and mass conversion of the thermoplastic sample.

LDPE Reactant (wo ) 15 g

Pyrolysis oil volume (density 1.22 g/cm3 ) 7 mL (8.54 g)
Experimental Results
Hydrocarbon gases 5.68 g
Tar content 0.78 g
α = 0.569 (56.9 wt %)

5. Discussion
The DC thermal plasma can achieve a thermal density of 0.129 MJ/m3 which satisfies the
activation energy required for the pyrolysis of 15 g of LDPE. The DC thermal plasma also reaches the
required operating temperature (i.e., above 625 ◦ C) faster in comparison with other heating sources.
The LDPE sample yielded 56.9 wt % fuel oil which consisted of 87.5 wt. % 1,4-dichlorobenzene,
toluene, undecane and xylenes as well as C10 and, C16 fractions. The tar content was 5.2 wt. % and
the gaseous emissions were tested for flammability, proving the hydrocarbon nature of the rest of
the products formed. The chlorine ions contamination might be due to using potable water from
condensation of hydrocarbon gaseous products which contains chlorine ions. The lower product yield
of liquid hydrocarbons from LDPE pyrolysis can be due to the higher operating temperature of DC
thermal plasma which favors formation of light gaseous hydrocarbons due to a higher rate of thermal
cracking [40]. This process system is more favorable than other pyrolysis systems which rely on gas
burners for pyrolysis reactions due to the absence of environmental emissions and higher temperature
controllability of the DC thermal plasma. Overall, the DC thermal plasma shows the ability to be
used for LDPE pyrolysis and can provide the needed thermal energy with a constant heating rate
as required.

6. Conclusions
This work illustrates the integration of a DC controllable thermal plasma circuit to be used in
thermoplastic to oil conversion reactions. While pyrolysis reactions consume a large amount of thermal
energy (around 1047 KJ/Kg of LDPE), the thermal plasma can meet the thermal requirements without
fuel emissions like gas burners. Also, the plasma temperature provides a constant heating rate of
7.8 ◦ C/min which prevents tar formation and increases the stability of the resulting pyrolysis oils.
In the experimental setup, a 270 W DC thermal plasma is used for a 15 g LDPE sample and pyrolysis
oils were collected for a product yield of 56.9 wt. %. The pyrolysis oil sample shows butyl-benzene as
a major product and the existence of small traces of decane diesel range oil. The DC thermal plasma
system can be used to replace other heating sources in pyrolysis reactors.

Acknowledgments: Authors would like to thank Janak Handa—Chief Operating Officer, Pro-Flange Limited for
their support to this research work.
Author Contributions: Hossam A. Gabbar and Mohamed Aboughaly conceived and designed the experiments;
Mohamed Aboughaly and C.A. Barry Stoute performed the experiments; Hossam A. Gabbar and Mohamed
Aboughaly analyzed the data and wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
DRO Diesel range oil
GC-FID Gas chromatography-Flame ionization detector method
LDPE Low density polyethylene
Energies 2017, 10, 784 13 of 15

Nomenclature
CT Total Capacitance (F)
Ea Activation energy (KJ/mol)
k Reaction constant (1/s)
ko Reactant constant at standard pressure and temperature
L Length of inductance (unit: Henry kg m2 s−2 A−2 )
pF Pico (10−12 ) Farad (s4 × A2 × m−2 × kg−1 )
Tp Plasma temperature (◦ C)
R Ideal gas constant (atm/mol·K)
wo Mass of initial LDPE sample (g)
wt Mass of unreacted LDPE sample (g)
w∞ Mass of reactant residue(g)
τ Reaction residence time(min)
dx
dt Conversion rate with respect to time (g/s)
α conversion of reactants to liquid oil products (g)

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