Fuel 92 (2012) 327–339

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

Microwave-heated pyrolysis of waste automotive engine oil: Influence

of operation parameters on the yield, composition, and fuel properties
of pyrolysis oil
Su Shiung Lam a,c,⇑, Alan D. Russell a, Chern Leing Lee b, Howard A. Chase a
a
Department of Chemical Engineering and Biotechnology, University of Cambridge, New Museums Site, Pembroke Street, Cambridge CB2 3RA, United Kingdom
b
BP Institute, Bullard Laboratories, University of Cambridge, Madingley Road, Cambridge CB3 0EZ, United Kingdom
c
Department of Engineering Science, University Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia

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

Article history: The pyrolysis of waste automotive engine oil was investigated using microwave energy as the heat
Received 17 May 2011 source, and the yield and characteristics of the pyrolysis oils (i.e. elemental analysis, hydrocarbon com-
Received in revised form 11 July 2011 position, and potential fuel properties) are presented and discussed. The microwave-heated pyrolysis
Accepted 13 July 2011
generated an 88 wt.% yield of condensable pyrolysis oil with fuel properties (e.g. density, calorific value)
Available online 28 July 2011
comparable to traditional liquid transportation fuels derived from fossil fuel. Examination of the compo-
sition of the oils showed the formation of light aliphatic and aromatic hydrocarbons that could also be
Keywords:
used as a chemical feedstock. The oil product showed significantly high recovery (90%) of the energy pres-
Pyrolysis
Microwave pyrolysis
ent in the waste oil, and is also relatively contaminant free with low levels of sulphur, oxygen, and toxic
Waste oil PAH compounds. The high yield of pyrolysis oil can be attributed to the unique heating mode and chem-
Pyrolysis oil ical environment present during microwave-heated pyrolysis. This study extends existing findings on the
Fuel effects of pyrolysis process conditions on the overall yield and formation of the recovered oils, by dem-
onstrating that feed injection rate, flow rate of purge-gas, and heating source influence the concentration
and the molecular nature of the different hydrocarbons formed in the pyrolysis oils. The microwave-
heated pyrolysis can be performed in a continuous operation, and the apparatus described which is fitted
with magnetrons capable of delivering 5 kW of microwave power is capable of treating waste oil at a feed
rate of 5 kg/h with a positive energy ratio of 8 (energy content of hydrocarbon products/electrical energy
supplied for microwave heating) and a net energy output of 179,390 kJ/h. Our results indicate that micro-
wave-heated pyrolysis shows exceptional promise as a means for recycling and treating problematic
waste oil.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction concerns over environmental pollution, and the difficulties and

The production of waste automotive engine oil is estimated at
24 million tons each year throughout the world, posing a signifi-
cant treatment and disposal problem for modern society. The
waste oil, containing a mixture of aliphatic and aromatic hydrocar-
bons, also represents a potential source of high-value fuel and
chemical feedstock. The preferred disposal options in most coun-
tries are incineration and combustion for energy recovery, and vac-
uum distillation and hydro-treatment for re-refining the waste oil
[1]. However, these disposal routes recover only the chemical value
of the waste and they are becoming increasingly impracticable as
⇑ Corresponding author at: Department of Chemical Engineering and Biotech-
nology, University of Cambridge, New Museums Site, Pembroke Street, Cambridge
CB2 3RA, United Kingdom. Tel.: +44 (0)1223330132; fax: +44 (0)1223334796.
E-mail addresses: ssl28@cam.ac.uk, sushiung@gmail.com (S.S. Lam), ar508@
cam.ac.uk (A.D. Russell), cll44@cam.ac.uk (C.L. Lee), hac1000@cam.ac.uk (H.A.
Chase).
additional costs of sludge disposal [2,3] are recognised due to the
undesirable contaminants present in waste oil [1].
Pyrolysis techniques have recently shown great promise as an
economic and environmentally friendly disposal method for waste
oil [4–6] – the waste material is thermally cracked and decom-
posed in an inert atmosphere, with the resulting pyrolysis oils
and gases able to be used as a fuel or chemical feedstock, and
the char produced used as a substitute for activated carbon, though
such practice is yet to become popular. The pyrolysis oil produced
is of particular interest due to its easy storage and transportation
as a liquid fuel or chemical feedstock. The oil can be catalytically
upgraded to transport-grade fuels, or added to petroleum refinery
feedstocks for further processing [7]. Most of the literature reports
focus on pyrolysis using conventional electric resistance and elec-
tric arc heating [4,6,8,9]. However, microwave-heated pyrolysis
has recently shown promise as a route to treating and recycling
of waste oil [7]; the advantages of microwave-heated pyrolysis

0016-2361/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.07.027
328 S.S. Lam et al. / Fuel 92 (2012) 327–339
have been elaborated in previous work [5] and will not be dupli-
cated here. In this process, waste oil is mixed with highly micro-
wave-absorbent material such as particulate carbon. As a result
of microwave heating, the oil is thermally cracked in the absence
of oxygen into shorter hydrocarbon chains. The resulting volatile
products are subsequently recondensed into pyrolysis oils of dif-
ferent composition depending on the reaction conditions. The use
of microwave radiation as a heat source is known to offer addi-
tional advantages over traditional thermal heat sources [5,10],
and the combination of carbon-based material and microwave
heating in pyrolysis processes is a fairly novel subject that is of
increasing interest as reflected by the increasing amount of re-
search reported in the literature [7,11,12]. Microwave radiation
provides a rapid and energy-efficient heating process compared
to conventional technologies. The diffuse nature of the electromag-
netic field allows microwave heating to evenly heat many sub-
stances in bulk, thereby offering an improved uniformity of heat
distribution, excellent heat transfer, and providing better control
over the heating process. Other advantages include higher power
densities and the ability to reach high temperatures at faster heat-
ing rates, facilitating increased production speeds and decreased
production costs. Furthermore, energy is targeted only to micro-
wave receptive materials and not to air or containers within the
heating chamber. It can promote or accelerate certain chemical
reactions by selectively heating the reactants, leading to a more
uniform temperature profile and improved yield of desirable prod-
ucts. The process is physically gentle, allowing for a wide variety of
applications in diverse fields.
This study investigates the influence of process parameters
(feed injection rate, purge gas flow, and heating source) on the
yield and characteristics of the pyrolysis oils produced from micro-
wave-heated pyrolysis of the waste oil, with a focus on their ele-
mental and hydrocarbon composition, and potential fuel
properties. These evaluations are important to assess the technical
feasibility and applicability of the pyrolysis process as a route to
energy recovery/feedstock recycling from waste oil. There have
been no reports on the composition of the oil products resulting
from microwave-heated pyrolysis of waste oil, and limited infor-
mation is available concerning the influence of key process param-
eters on the pyrolysis of waste oil, although a few studies have
been performed on electric resistance heated pyrolysis of waste
oil [6,13–15].
Fig. 1. Schematic layout of microwave-heated pyrolysis system.
2. Experimental section
2.1. Materials
Shell 10 w-40 motor oil was used throughout the experiments.
The waste oil was sampled from the crankcase of diesel engines
run on unleaded fuel. The hydrocarbon composition of the waste
oil, the particulate carbon (TIMREX FC250 Coke, TIMCAL Ltd., Bod-
io, Switzerland) used as microwave absorbent to heat the waste oil,
and their pre-experimental treatment have been reported in previ-
ous works [5,7]. Before pyrolysis, the waste oil samples were fil-
tered such that the size of any remaining particulates (i.e. metal
particles, carbon soots, and other impurities) were less than
100 lm; samples were examined for C, H, N, S, O content by ele-
mental analysis; calorific value was determined by bomb
calorimetry.
2.2. Experimental details
The experimental apparatus for this investigation has been de-
scribed in detail in previous work [5]. The only change from this
description is the addition of a mixed-cellulose-ester membrane
filter (0.45 lm ME25 filter, Schlecher & Schuell, Germany) (see
(5) in Fig. 1) to remove any metallic solid residues present in the
pyrolysis volatiles before they passed through the condensation
system. The refined experimental apparatus is shown in Fig. 1.
Microwave-heated pyrolysis of waste oil was performed in a
bell-shaped quartz reactor (180  180  180 mm) (2) filled with
1 kg of particulate carbon, which is stirred (3) and heated by a
5 kW microwave oven (1) at a heating rate of about 60 °C/min over
a range of pyrolysis temperatures (250–700 °C), feed injection
rates (0.4–5 kg/h) and purge gas flows (0.1–0.75 L/min) to under-
stand the influence of these process parameters on the final pyro-
lysis oils obtained; N2 purge-gas was vented through the system to
maintain the apparatus in an inert nitrogen atmosphere, and the
particulate carbon, added initially into the reactor in one batch,
was stirred to ensure a uniform temperature distribution through-
out the reactor and to maximise heat transfer during pyrolysis. The
waste oil is nearly transparent to microwaves due to its non-polar-
ity nature, therefore it requires heating by contact with microwave
absorbent materials (e.g. carbon-based materials such as particu-
late carbon) in order to achieve pyrolytic thermal cracking. The
 S.S. Lam et al. / Fuel 92 (2012) 327–339
sample of waste oil was continuously added to the reactor (4) at
each target feeding rate over a period of 2 h as soon as the target
pyrolysis temperature was achieved; it was previously ascertained
that the magnetron system of the microwave oven was able to gen-
erate sufficient heat to maintain the desired target temperature at
all these flow rates. Products generated in the pyrolysis reaction,
termed generally as pyrolysis volatiles (consisting of a mixture of
hydrocarbon gases, liquids, and suspended solids existing in a va-
pour phase), leave the reactor and pass through a condensation
system (6, 7, 8, 9), and either condense into pyrolysis oil (10, 11)
or are sampled as incondensable pyrolysis gases (13, 14) before
being vented from the system.
The amount of residue material not converted to gaseous or li-
quid products was determined by measurement of the weight
change in the reactor and its contents before and after the reaction.
The residue materials are likely to be chars produced from tertiary
cracking reactions of the pyrolysis process [7]; these were particles
that possessed a harder texture, darker colour, and most of which
had a smaller size than the particulate carbon used in the bed of
the reactor. These chars, which mostly accumulated on the surface
of the carbon bed, were separated from the carbon particles using
sieves (90 and 250 lm) and mixed with the metallic residues
deposited on the ME25-filter installed between the reactor and
the condensation system for later analysis. The yield of pyrolysis
oil was determined by measuring the weight increase in the col-
lecting vessels and filter. The pyrolysis oil was then transferred
into glass bottles until further analysis (see Section 2.4). The gas
yield was determined by mass balance and assumes that whatever
mass of added sample that is not accounted for by the residue and
pyrolysis oil measurements left the system in gaseous form. All the
pyrolysis experiments were repeated several times and the data re-
corded is the average of the results obtained from three valid re-
peated runs performed under identical conditions. These runs
showed good reproducibility and precision with low standard
deviations shown in the product yield (±1–5 wt.%). The virgin oil
(FO), the waste oil, and the pyrolysis oils were examined for hydro-
carbon composition by gas chromatography coupled with a mass
selective spectrometry detector (GC–MS) and a flame ionisation
detector (GC-FID). These oil samples were also analysed by Fourier
Transform Infrared Spectroscopy (FTIR) and elemental analyzer to
identify their chemical functional group and elemental content (C,
H, N, S, and O). In addition, the fuel properties of these oil samples
(i.e. calorific value, density, flash point, viscosity, boiling point dis-
tribution) were determined according to ASTM standard methods
(see Section 2.4).
2.3. Temperature measurement
The temperature of the carbon bed in the system was moni-
tored using two thermocouples; one ducted into the middle layer
of the carbon bed through the centre of the shaft that protrudes
from the bottom of the stainless steel stirrer shaft, the other enters
the reaction chamber through a side port on the top of the reactor
and is positioned at the top of the carbon bed. Both thermocouples
remain in direct contact with the carbon inside the reactor. In addi-
tion, ferrite core thermocouple connectors and cable clamps were
used to reduce the electromagnetic interference caused by the
microwaves on the temperature measurement.
Accurate measurement of the evolution of the temperature of
the carbon bed was difficult during the heating process – firstly,
there are inherent difficulties involved in measuring this parame-
ter in microwave devices [16]; secondly, it should be noted that
the temperature is not uniform throughout the carbon bed during
the initial heating to the target temperature; electrical arcing was
found to occur for a relatively short period at the beginning of the
heating process, but it stopped when the carbon bed had been
329
heated to the target temperature. A stirred bed reactor is used in
this study in which the physical movement and mixing of carbon
particles by the stirring system creates a uniform temperature dis-
tribution, independent of the penetration depth of the microwaves
into the bed of particulate carbon. Provided the temperature is
kept consistent and uniform in this system, once the thermal equil-
ibration and steady state temperature were reached, the tempera-
ture shown by the thermocouples are assumed to give a reliable
reading of the average temperature of the bulk carbon bed.
2.4. Analytical methods
Oil samples were analysed using a 6890/5973 GC–MS instru-
ment (Agilent Technologies, Palo Alto, CA), allowing the quantifica-
tion of compounds by both species and size; compounds were
identified using the NIST 2005 mass spectral library using similar-
ity indices of >70%, or by comparison with published GC–MS data
for similar products; the detailed description of this analytical
method have been reported in previous work [7] For polycyclic
aromatic hydrocarbons (PAHs), the GC–MS instrument was pro-
grammed into selected-ion-monitoring (SIM) mode and the peaks
were compared to external PAH standards for quantification. In
addition to GC–MS analysis, the oils were analysed by the 6890
gas chromatograph coupled with a flame ionisation detector, using
a 30 m HP-5 capillary column (5% phenyl methyl silicone, I.D.
0.53 mm, film thickness 5 lm). The GC-FID oven was programmed
from 40 °C, held for 5 min, then ramped at 5 °C/min to 280 °C with
a final holding time of 30 min. Quantification of compounds on the
GC-FID was obtained by external standard method and relative
retention times once the component has been identified by the
GC–MS analysis. The data obtained from GC-FID were used to eval-
uate the simulated distillation curves of the various oil samples
according to ASTM D2887-08 [17].
Elemental analyses of oil samples were performed using a LECO
CHNS-932 elemental analyzer (LECO Corporation, Michigan, USA).
Samples were burned at 1000 °C in a flowing stream of oxygen. The
products of combustion (CO2, H2O, N2 and SO2) then passed
through the system with He as the carrier gas, and their content
of carbon, hydrogen, and sulphur were measured quantitatively
by selective IR absorption detectors, except for the nitrogen, which
was measured by a thermal conductivity detector. Oxygen content
was measured by pyrolysing a separate sample at 1300 °C in a VTF-
900 pyrolysis furnace (LECO Corporation, Michigan, USA). The oxy-
gen released in the pyrolysis reaction then reacts with activated
charcoal to form CO, which was converted to CO2 by passing
through an oxidation tube with He as the carrier gas. The CO2 gen-
erated was then measured as above by an IR detector. The analysis
of chemical functional group in oil samples was performed using a
Bruker Tensor 27 FTIR Spectrometer (Bruker Optics, Ettlingen, Ger-
many) that produces IR spectra for each sample.
Experimental analysis of the fuel properties of the oil samples
was performed according to the following ASTM methods:
D1298-99(2005) [18] for density, D1310-01 [19] for flash point,
and D445-10 [20] for viscosity. The boiling point distribution of
hydrocarbons in oil samples were determined using the 6890
GC-FID instrument by a simulated distillation method according
to ASTM D2887-08 [17] and ASTM D3710-95(2009) [21]; the sam-
ple was heated from ambient temperature to 550 °C (300 °C for
ASTM D3710-95) at a heating rate of 10 °C/min with high purity
He gas vented through the apparatus at a flow rate of 0.1 L/min.
Oil samples were also analysed for calorific value using a Parr
6200 Isoperibol bomb calorimeter (Parr Instrument, Moline, Illi-
nois). Detailed analysis and sample preparation were performed
according to ASTM Standard D4809-09a. [22] The solid content
(ethanol-insoluble) was determined by filtering the pyrolysis oil
through a 0.1-lm polycarbonate membrane filter (Milipore Co.,
330 S.S. Lam et al. / Fuel 92 (2012) 327–339

Billerica, MA) and measurement of the weight change before and

after filtration.

3. Results and discussion

In this study, different process parameters were studied to

determine the optimum conditions that provide the greatest yield
of pyrolysis products containing highly desired compounds (e.g.
commercially valuable light hydrocarbons), and to investigate the
effects of these parameters on the compositions of pyrolysis prod-
ucts, with a special emphasis on the pyrolysis oil. The main objec-
tive was to convert the waste oil to petrochemical products
suitable for use as a fuel or raw chemical feedstock. This paper ex-
plored the effects of varying the feed injection rate of waste oil, and
the purge gas flow rate. The investigation of pyrolysis products at
different temperatures have been reported in our previous works
[5,7]. Pyrolysis at a constant temperature of 550 °C was used as
throughout based on the optimum temperature obtained in the
previous work [7] that showed the greatest yield of valuable light
hydrocarbons and only low levels of residual metals in the pyroly-
sis oil.

3.1. Product yield

Fig. 2 outlines the effect of N2 purge rate and waste oil feed rate
on the fraction of waste oil converted to pyrolysis gases, pyrolysis
oils, and char residues. Increasing the N2 purge rate from 100 to
250 ml/min resulted in an increased yield of pyrolysis oil. The in-
crease in waste oil feed rate demonstrated a minor influence on
the yield of pyrolysis oil, as the total increase in the yield of pyro-
lysis oil resulting from the increase in waste oil feed rate from 0.4
to 5 kg/h was only 4%. The slight upward trend in yield could be
due to experimental error as a maximum error rate of 5 wt.%
was observed in the values of the product yields (see Section 2.2),
but it is thought that this could be a real trend expected from the
increase in waste oil feed rate. When the hydrocarbons in waste oil
undergo cracking into shorter molecules, which then vaporise as
pyrolysis volatiles, the volume increase accompanying the phase
change from liquid to vapour creates an increase of pressure in
the reactor that drives the pyrolysis volatiles out of the reactor into
the product collection system. At higher waste oil feed rates, this
process is likely to occur more rapidly and more molecules are
likely to enter the vapour phase earlier, causing a more rapid flow
of pyrolysis volatiles out of the reaction ‘hot zone’ inside the reac-
tor. It is also believed that the higher rates of N2 purge gas resulted
in a more rapid flow of pyrolysis volatiles out of the reactor due to
the higher pressure created in the reactor. The residence time of
pyrolysis products in the reactor thus becomes dependent on these
two process parameters, which leads to shorter residence times of
the pyrolysis volatiles in the reactor at higher purge and feed rates.
The decrease in residence time decreases the exposure of pyrolysis
volatiles (evolved from the waste oil compounds) to secondary
reactions (e.g. secondary thermal cracking to form pyrolysis gases,
tertiary cracking and repolymerisation to form chars) and leads to
higher yield of pyrolysis oil and smaller yields of both pyrolysis
gases and residues (likely to be char) observed under these condi-
tions; similar findings were reported by other workers [23]. At very
high N2 purge rates (750 ml/min), the yield of pyrolysis oil de-
creases, suggesting that the installed condensation system is un-
able to condense the pyrolysis volatiles at this considerably
faster vapour flow rate, which leads to a higher corresponding
yield of pyrolysis gases. The slightly higher amounts of residues
observed at higher feed rates (P2.5 kg/h) could be attributed to
the formation of residues such as char and residual unpyrolysed
waste oil, the amounts of which are likely to increase at higher feed
Fig. 2. Product yields (wt.%) as a function of N2 purge rate (up) and waste oil feed
rate (bottom). Process conditions: pyrolysis at a constant waste oil feed rate of
0.4 kg/h was used when the effects of varying the N2 purge rate were studied,
whereas a constant N2 purge rate of 250 ml/min was used to study the effects of
varying the waste oil feed rate, and all experiments were performed at a constant
temperature of 550 °C.
rates. The results show that extended heating of the generated
pyrolysis volatiles in the reactor could promote different product
compositions due to secondary reactions of the primary pyrolysis
product; hence it was observed that some waste oil is consumed
in the production of pyrolysis gases and char in addition to pyroly-
sis oil.
The waste oil feed rate, when compared with the mass of the
microwave absorbent (in this case particulate carbon), provides
useful information for chemical reactor design by assessing the
weight hourly space velocity (WHSV) of the pyrolysis process.
The WHSV, defined as the waste oil feed rate divided by the mass
of particulate carbon, was calculated based on the different waste
oil feed rates. The variation of the yield of pyrolysis oil with this
parameter is presented in Fig. 3. The results show that the pyroly-
sis reactor is able to process each hour a waste oil feed up to five
times the mass of the particulate carbon while maintaining a rela-
tively high production of pyrolysis oil from the feed (85–88 wt.%).
The use of a microwave-heated bed of particulate carbon in this
set-up showed good heat transfer and cracking capacity to pyro-
lyse the waste oil. The microwave energy is targeted to and heats
mainly the microwave-receptive particulate carbon which in turn
transfers thermal energy to the waste oil added into the carbon
 S.S. Lam et al. / Fuel 92 (2012) 327–339 331

Fig. 4. Comparison of oil yield in waste oil pyrolysis processes heated with different
media (waste oil only [6,8,13,44–46], coal [47,48], scrap tires [15]), and by different
Fig. 3. The yields (wt.%) of pyrolysis oil in relation to weight hourly space velocity heating system (microwave heating, conventional electric heating).
(h 1).

been observed during the treatment of other types of waste [24–

bed in order for pyrolysis to occur [5]. Overall, the waste oil feed 26]. These results suggest that the pyrolysis of waste oil is influ-
rate was found to have little influence on the yields of pyrolysis enced by the heating system (heating source, heating media) in
product (Fig. 2), indicating the potential of this pyrolysis process addition to the other factors commonly reported in literature
in treating high volumes of waste oil while maintaining a relatively (e.g. feed composition and flow rate, catalyst, temperature,
high throughput of pyrolysis oil (Fig. 3). pressure).
The highest yield of pyrolysis oil (88 wt.%) was observed at
250 ml/min of N2 purge rate, and 5 kg/h of waste oil feed rate
3.2. Visual inspection of pyrolysis operation
(Fig. 2). It is assumed that this represents the optimum balance be-
tween sufficiently high purge and feed rates to sweep the evolved
The conversion of waste oil to pyrolysis oil started to occur
pyrolysis volatiles out of the reactor, thus producing condensable
when the operating temperature was above 400 °C, where over
vapours (pyrolysis oil) by avoiding the promotion of secondary
50 wt.% of the product was a viscous oil mixture. The maximum
reactions that would result in increased formation of incondens-
conversion of waste oil was accomplished at 550 °C, during which
able gases and char residues, while not being so high that the con-
P67 wt.% of the waste oil was transformed into pyrolysis oil
densation system was unable to condense the pyrolysis volatiles. It
(Fig. 2). The pyrolysis oil obtained at 550 °C was a fairly pale yel-
should be noted that 5 kg/h is the highest waste oil feed rate that
lowish-gold hydrocarbon liquid (Fig. 5) containing a small amount
can be processed in this experimental device as it was ascertained
of dark solids. It is thought that these solids derived from the small
that the 5 kW magnetron system of the microwave oven could no
quantities of very fine carbon particles originally present in the
longer generate sufficient heat to maintain the desired operating
pyrolysis reactor; these are likely to escape from the reactor and
temperature (550 °C) at flow rates of 6 kg/h and above. Our results
co-migrate with the pyrolysis oil. These particles can be removed
have shown that a recovery of pyrolysis oil of approximately 84–
88% of the initial mass of waste oil is possible under these
conditions.
Fig. 4 compares our results to those of waste oil pyrolysis pro-
cesses heated by conventional electric heating either using waste
oil on its own or in the additional presence of coal or scrap tyres.
The use of the microwave-heated bed of particulate carbon, com-
pared to the other methods of operation, seemed to have a benefi-
cial effect in cracking the waste oil to produce higher amounts of
condensable products. This may be attributed to the different heat
distributions present during microwave-heated pyrolysis. The ap-
plied microwave radiation heats mainly the carbon, creating a
localised reaction ‘hot zone’ as opposed to conventional electric
heating which is externally applied to the reactor and heats all
the substances in the reactor including the evolved pyrolysis vola-
tiles and gases. In conventional heating, the pyrolysis volatiles,
being in a larger reaction ‘hot zone’ than occurs during microwave
heating, are likely to undergo increased secondary reactions (i.e.
secondary thermal cracking) and this leads to a higher yield of
pyrolysis gases and a lower yield of pyrolysis oil. Similar differ-
ences between conventional and microwave pyrolysis have also Fig. 5. Pyrolysis oil from microwave pyrolysis of waste oil.
332 S.S. Lam et al. / Fuel 92 (2012) 327–339

by filtration. The pyrolysis oil was observed to be much less dense
and viscous compared to the waste oil, indicating the cracking of
heavy hydrocarbon chains in the waste oil to lighter fragments
by the microwave-heated pyrolysis.
3.3. Chemical composition
GC–MS analysis revealed that both virgin and waste oils are
formed from a mixture of low and high molecular weight aliphatic
and aromatic hydrocarbons (Table 1). The majority of the hydro-
carbon compounds were in the C21–C45 range for virgin oil, but
only C11–C40 were detected in waste oil (Table 1). This concurs
with previous findings [5,7] that suggest the conversion of a frac-
tion of heavier hydrocarbons (originally present in unused virgin
oil) to lighter hydrocarbons while acting as lubricant in engine
operation.
Quantitative analyses of the pyrolysis oils were undertaken and
the results are presented in Table 1. The compounds present were
grouped into different classes of organic compounds, i.e. naphth-
enes (cycloalkanes), alkanes, alkenes, aromatics, and unknowns
(unidentified peaks). It should be noted that analysis of some of
the oil samples showed over one hundred peaks, however only
the compounds present at 0.5 wt.% and above are presented in
the results.
The study showed that the waste oil, containing C11–C40 hydro-
carbons, was thermally cracked to oil products comprising mainly
of C5–C30 hydrocarbons, and which were dominated by aliphatic
hydrocarbons (50–71 wt.%) and significant amounts of aromatics
(23–42 wt.%). This indicates the occurrence of cracking of com-
pounds to produce some aromatic structures, possibly derived
from cyclisation and aromatisation reactions that occurred during
pyrolysis. The aliphatic hydrocarbons were mostly alkanes (31–47
wt.%), and alkanes from pentane to decane were present at the
highest concentrations. Alkenes (9–23 wt.%), with carbon chain
lengths ranging from C5 to C15, were also present, with heptene
to decene being the most abundant. These aliphatic hydrocarbons,
particularly the C5–C20 aliphatic fractions, represent a potentially
high-value chemical feedstock or fuel source. The alkanes could
be upgraded to produce transport-grade fuels, or gasified to com-
mercially valuable gaseous products including hydrogen, whereas
the alkenes are highly desired feedstocks in petrochemical indus-
try, especially in plastic manufacture.
The pyrolysis oils were found to contain many different lengths
of aliphatic chains, showing that waste oil was randomly cracked
into short fragments of different carbon chain lengths. The wide
distribution of aliphatic chains in the pyrolysis oils suggested that
the thermal cracking of waste oil in this process predominantly fol-
lows the free-radical-induced random scission mechanism [27–
30]. This mechanism may have led to the production of hydrocar-
bon radicals that were stabilised by capturing the hydrogen atoms
from nearby molecules, producing alkanes and alkenes via the free
radical and b-scission reactions. Heavy n-alkanes and alkenes were

Table 1
Main chemical components (wt.%) of the virgin oil (FO), the waste automotive engine oil (WO), and the pyrolysis oils produced under various conditions.

FO WO Pyrolysis oil
N2 purge rate (ml/min)a WO feed rate (kg/h)a
100 250 750 0.4 1 2.5 5
Aliphatics
Alkanes 89.7 91 31.4 39.6 47 39.6 40.4 42 43.9
Naphthenes (Cycloalkanes) 0.5 0.5 10.2 7.6 1.4 7.6 6.5 5.7 3.9
Alkenesb 0.8 0.5 8.6 17.7 22.6 17.7 18.2 18.8 20.1
Total 91 92 50.2 64.9 71 64.9 65.1 66.5 67.9
Carbon components
C5–C10 –c – 29 32 20.4 32 29.2 24.4 21.5
C11–C15 – 3 13.2 15 14.3 15 14.8 14.9 13.4
C16–C20 – 7 7 13.3 18.2 13.3 15.2 17.9 18.8
C21–C30 60 57 1 4.6 18.1 4.6 5.9 9.3 14.2
C31–C40 29 25 – – – – – – –
C41–C45 2 – – – – – – – –

Aromatics
Benzene (C6H6) – – 11.8 6.6 2.1 6.6 4.5 4.1 3.5
Toluene (C7H8 – – 11.9 7.8 2.3 7.8 5.6 4.7 3.4
Xylene (C8H10) – – 9.4 7.1 3.6 7.1 6.2 5.4 4.7
Alkylbenzenesd 0.5 1.1 8.4 8.2 14.6 8.2 12.8 13.1 13.9
Total 0.5 1.1 41.5 29.7 22.6 29.7 29.1 27.3 25.5

PAHs
Naphthalene 0.03 0.1 0.41 0.23 0.13 0.23 0.17 0.10 0.12
Acenaphthene – – 0.09 0.03 0.02 0.03 0.02 0.02 0.02
Acenaphthylene – – 0.08 0.04 0.02 0.04 0.02 0.02 0.02
Phenanthrene 0.003 0.01 0.07 0.04 – 0.04 0.03 0.01 0.01
Anthracene – – 0.16 0.11 0.03 0.11 0.06 0.05 0.03
Pyrene 0.002 0.02 0.09 0.05 – 0.05 – – –
Total 0.035 0.13 0.9 0.5 0.2 0.5 0.3 0.2 0.2
Otherse 8.5 6.8 7.4 4.9 5.8 4.9 5.5 6.0 6.4
a
Process conditions: pyrolysis at a constant WO feed rate of 0.4 kg/h was used when the effects of varying the N2 purge rate were studied, whereas a constant N2 purge rate
of 250 ml/min was used to study the effects of varying the WO feed rate, and all experiments were performed at a constant temperature of 550 °C.
b
Alkenes: n-alkenes, dialkenes.
c
Not detectable.
d
Alkylbenzenes: ethylbenzene (C8H10), allylbenzene (C9H10), propylbenzene (C9H12), trimethylbenzene (C9H12), 1,3-Diethylbenzene (C10H14), 1-methyl-2-propylbenzene
(C10H14), and hexyl-benzene (C12H18).
e
Unknown compounds due to unidentified peaks.
 S.S. Lam et al. / Fuel 92 (2012) 327–339 333

then cracked to form lighter compounds. This accounts for the al-
kanes, naphthenes, and alkenes observed for each carbon number
across all collected samples.
Valuable light aromatics such as BTX (the sum of benzene, tol-
uene, and xylene) were found in significant quantities (8–33 wt.%)
in the pyrolysis oils. The aromatics were composed mainly of sin-
gle ring alkyl aromatics, including benzene derivatives such as 1,3-
diethylbenzene, 1-methyl-2-propylbenzene, and hexyl-benzene, as
well as benzene rings with short alkyl groups – mainly toluene,
ethyl-benzene, and xylene. The subsistent chains attached to the
benzene rings ranged from C1 to C6 groups and were mostly non-
branched saturated compounds. Polycyclic aromatic compounds
(PAHs) were observed in the pyrolysis oil but only in minor quan-
tities (60.9 wt.%). Several sulphur and/or nitrogen-containing com-
pounds such as thioureas, amines, and benzothiazoles were also
detected in the pyrolysis oils, but the quantities were low (60.1
wt.%) and were therefore not presented in the table.
In this study, the decrease in purge and feed rates was thought
to lead to an increased residence time of the pyrolysis volatiles in
the reactor, resulting in an increase in aromatic content along with
a decrease in aliphatic content in the pyrolysis oils, and the ali-
phatic and aromatic content improved towards smaller hydrocar-
bon chains. The amounts of alkanes and alkenes were reduced in
favour of aromatic formation (including PAHs). This agrees with
the findings in previous works [5,30,31], which propose that an in-
crease in residence time may promote secondary reactions of
hydrocarbons (e.g. cyclisation and aromatisation) in the pyrolysis
volatiles to form aromatics; the production of aromatics by these
secondary reactions have also been reported in pyrolysis studies
of pure hydrocarbon compounds [32,33]. The aromatics are likely
to be formed via Diels–Alder type secondary reactions, which in-
volve dehydrogenation and cyclisation of alkenes (produced from
pyrolysis cracking of waste oil) to form aromatic hydrocarbons.
These secondary reactions are likely to occur in this microwave-
heated pyrolysis in a manner similar to that reported in other pyro-
lysis processes [25,34], since n-alkenes and dialkenes (e.g. 1.3-
butadiene) were found in the pyrolysis oils (Table 1). Furthermore,
the decreased concentrations of alkenes at low purge and feed
rates (Table 1) suggest that it was the increased occurrence of
these Diels–Alder type secondary reactions that had combined
and converted the n-alkenes and dialkenes into aromatics, leading
to increased formation of benzene, toluene, and alkylbenzenes. The
main products formed by the Diels–Alder type reactions in pyroly-
sis cracking are reported to be benzene, toluene, and alkylbenzenes
[27,33,34], and these compounds were detected in the pyrolysis
oils obtained in this study, supporting the proposed reaction mech-
anism for the formation of aromatics. Depending on the degree of
aromatisation, condensation reactions of the ring structure of the
aromatic compounds may occur subsequently and result in
formation of heavier aromatics such as PAHs [25,34]; the detection
of PAHs in the pyrolysis oils (Table 1) supports the proposed occur-
rence of condensation reactions for PAH formation.
The yield of pyrolysis oil was found to increase with increasing
waste oil feed rate, however, this reduced the yield of the desired
fraction of light aliphatic hydrocarbons (C5–C20) in the pyrolysis
oil. The pyrolysis oils formed under high feeding rate were found
to contain higher amounts of heavier hydrocarbon components
(>C20). At higher feed rates, the increased flow of pyrolysis volatiles
out from the reactor led to decreased participation of pyrolysis vol-
atiles (evolved from the waste oil compounds) in secondary reac-
tions (e.g. secondary thermal cracking) and helps to explain the
greater quantities of heavier hydrocarbon components in the pyro-
lysis oil. Moreover, it is thought that most of the heavier compo-
nents were obtained as a result of evaporation of some
components in the waste oil that escaped from the reactor without
being cracked [9]. The main implication is that a high waste oil
feed rate does not necessarily represent an ideal condition to pro-
duce valuable oil products with this microwave pyrolysis appara-
tus. The benefit of pyrolysing waste oil at high feed rates to
increase the yield of total oil product is negated by the significant
increase in the yield of undesirable heavier hydrocarbon compo-
nents (>C20) in the oil product under these conditions. Overall,
the results shows that the waste oil can be thermally cracked
and condensed to pyrolysis oils comprising valuable light aliphatic
and aromatic hydrocarbons, which could be treated and used as
either an energy source or valuable chemical feedstock.
3.4. Elemental composition
Table 2 shows the elemental composition of the waste oil before
pyrolysis treatment and the pyrolysis oils obtained at different
purge and feed rates. Carbon and hydrogen represented the main
elements present in waste oil, whereas nitrogen, sulphur, and oxy-
gen were detected in very low concentrations (62.1 wt.%). The car-
bon and hydrogen are mainly from the base oils from which the
lubricating oil is formulated, whereas nitrogen, sulphur and oxy-
gen are likely to originate from the additives (e.g. antioxidants)
present in the engine oil [2]. The low content of sulphur in the
waste oil suggests that sulphur originally present in engine oil is
likely to have reacted with oxygen in the air to form sulphur oxi-
des, which subsequently escape to the atmosphere during engine
operation.
The pyrolysis oils showed a much lower content of oxygen and
a significantly higher H/O atomic ratio than the waste oil. The oils
also showed a very low O/C atomic ratio, indicating the very low
level of oxygenation in the oils. The use of a bed of carbon as the
heating medium in our set-up, which also provides a reducing
chemical environment at the operational temperatures, appears

Table 2
Elemental analysis (wt.%) of the virgin oil (FO), the waste automotive engine oil (WO), and the pyrolysis oils.

FO WO Pyrolysis oil
N2 purge rate (ml/min)a WO feed rate (kg/h)a
100 250 750 0.4 1 2.5 5
C 82.7 81.7 88.6 85.6 85.7 85.6 85.1 84.9 84.6
H 12.5 15.1 11.2 14.2 13.7 14.2 14.3 14.5 14.6
N 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2
S 2.3 0.8 0.02 0.02 0.03 0.02 0.02 0.03 0.03
O 2.3 2.1 0.1 0.1 0.5 0.1 0.1 0.2 0.2
H/C (mol/mol) 1.8 2.2 1.5 2.0 1.9 2.0 2.0 2.0 2.1
H/O (mol/mol) 86 114 1778 2254 435 2254 2270 1151 1159
O/C (mol/mol) 0.02 0.02 0.001 0.001 0.004 0.001 0.001 0.002 0.002
a
Process conditions: pyrolysis at a constant WO feed rate of 0.4 kg/h was used when the effects of varying the N2 purge rate were studied, whereas a constant N2 purge rate
of 250 ml/min was used to study the effects of varying the WO feed rate, and all experiments were performed at a constant temperature of 550 °C.
334 S.S. Lam et al. / Fuel 92 (2012) 327–339
to decrease the formation of undesired oxidised species during the
pyrolysis, and thus leading to the decreased oxygen content in the
pyrolysis oil. This is desirable since oxidised species (e.g. acids and
reactive peroxides) may catalyse undesired polymerisation reac-
tions of unsaturated compounds in the pyrolysis oil during storage,
generating larger molecules (e.g. tar or sludge from polymerisation
of olefins) that have poor mutual solubility with other compounds
in the oil, resulting in increased viscosity and low heating value of
the oil. Any carbon that becomes oxidised as a result of redox reac-
tions is of little concern as it will usually be converted to CO or CO2
which then leaves the system in the gas phase. On the other hand,
it is likely that some metals in the waste oil may have reacted with
the oxygen present in the additives in waste oil [2] to form metal
oxides that are retained within the carbon bed during pyrolysis;
the presence of metals in the waste oil has been reported in previ-
ous works [5]. The reduction in oxygen content is also likely to be
due to decarboxylation commonly occurring during thermal treat-
ment processes; this agrees with the findings of Sinağ et al. [6] in
their waste oil pyrolysis study. The deoxygenation of oxygenated
species (e.g. phenols originating from the antioxidant additives in
the engine oil) to thermally stable aromatic compounds [34] is an-
other likely source of the reduction of oxygen content. The low
oxygen content in the pyrolysis oils represents a favourable feature
in producing a potential fuel source with high calorific value.
The H/C atomic ratio is a good indicator of the existence of
hydrocarbons in the waste oil and the pyrolysis oils, and the vari-
ations in the ratio indicate the different levels of saturation in the
CAC bonds. A decrease in H/C ratio was observed for pyrolysis oils
compared to the waste oil, suggesting that dehydrogenation and
aromatisation had occurred to some extent to form compounds
Fig. 6. FTIR spectrum (above) and the functional groups (bottom) detected in pyrolysis oil.
containing carbon double-bonds (e.g. alkenes, aromatics) with a
lower H/C ratio; the result is consistent with the hydrocarbon com-
position and functional groups found by GC–MS and FTIR analysis
(see Sections 3.3 and 3.5). The purge and feed rates seem to have
had only a minor influence on the elemental composition of the
pyrolysis oils; however, at lower purge rates, increased secondary
reactions as a result of the longer residence times of the pyrolysis
volatiles in the reactor are likely to increase the degree of random
scission thermal cracking and aromatisation as indicated by the
lower H/C ratio in the oils obtained under these conditions.
The pyrolysis oils contain a lower sulphur content compared to
the waste oil; this suggests that sulphur, although present in very
low concentrations in waste oil, is likely to have reacted with oxy-
gen during pyrolysis to form sulphur oxides. In addition, new sul-
phur compounds may be formed during pyrolysis, e.g. metal or
non-volatile inorganic sulphides [15,35], which remain in the car-
bon bed; these reactions lead to decreased sulphur content in the
pyrolysis-oils. In all cases the sulphur content of the pyrolysis oil
obtained (20–30 ppm) was found to meet internationally pre-
scribed standards for unleaded petrol (sulphur: 6150 ppm or
60.1 wt.%) and diesel fuels (sulphur: 6350 ppm or 60.1 wt.%),
e.g. European Fuels Directive 98/70/EC and UK Motor Fuels Regula-
tions 1999 [36], British Standard of Unleaded Petrol (BS EN
228:2008 [37]), and British Standard of Diesel (BS EN
590:2009+A1:2010 [38]). The use of fuel derived from these
low-sulphur pyrolysis oils can potentially lead to a reduction of
SOx emissions compared to fossil fuels (e.g. diesel). The results
from elemental analysis show that the microwave-heated
pyrolysis generated a pyrolysis oil with a low sulphur and oxygen
content, further indicating the potential of this pyrolysis process in
 S.S. Lam et al. / Fuel 92 (2012) 327–339 335

treating this kind of problematic waste oils. The low sulphur and
oxygen content is beneficial to upgrading the pyrolysis oil to trans-
port-grade fuels.
3.5. FTIR analysis
Fig. 6 shows the infrared spectrum of the pyrolysis oil obtained
by FTIR analysis and the general classification of chemical com-
pounds from the FTIR spectrum; the classification was defined
based on the degree of infrared absorption (or transmittance) de-
tected at different frequencies (or wave number) over the infrared
spectra obtained from the pyrolysis oils. The data presented show
typical results for the pyrolysis oils produced by microwave-
heated pyrolysis of waste oil as there was little difference in the
FTIR spectra obtained with the different process parameters (N2
purge flow and waste oil feed rate), except for a small variation
in the transmittance peak intensities detected at the different fre-
quency ranges. The results indicate that most of the hydrocarbons
found in the pyrolysis oils were alkanes, alkenes, and single-ring
aromatics.
Interestingly, compounds with OAH and C@O stretching vibra-
tions, such as phenols, aldehydes, carboxylic acid, showed very low
peak intensities, suggesting that these compounds were present
only in minor quantities in the pyrolysis oil. The very low charac-
teristic peaks of these compounds observed in the FTIR spectrum
provide useful information when assessing the extent of oxidation
that had occurred in the oils. Oil oxidation normally results in the
sequential addition of oxygen to base oil molecules, causing the
formation of oxygenated by-products with hydroxyl (OAH) and
carbonyl groups (C@O), e.g. aldehydes and carboxylic acids. Car-
boxylic acids, in particular, are undesirable as they are the common
cause of acidic corrosion and sludge formation (as a result of poly-
merisation in which carboxylic acids combine to form larger
molecular species), which can lead to increased oil viscosity and
causing problems such as filter plugging and system fouling. Over-
all, the trace amount of oxygenated compounds (e.g. aldehydes,
carboxylic acids) in the pyrolysis oils indicates that very little oil
oxidation occurred in this pyrolysis process; this corroborates the
low oxygen contents found in the pyrolysis oil by elemental anal-
ysis (see Table 2), and the beneficial effects of the carbon bed (act-
ing as a reducing reaction environment) in decreasing both the oil
oxidation and the resulting formation of undesired oxidised spe-
cies (see Section 3.4).
3.6. Fuel properties
The oil products derived from microwave-heated pyrolysis
were examined for their properties as a fuel and these values were
compared to those of the virgin oil, the waste oil, and gasoline col-
lected from a local petrol station (Table 3). The waste oil shows a
lower density but higher calorific value than the virgin oil. It is
thought that some of the heavier hydrocarbons in virgin oil were
decomposed into lighter hydrocarbons in waste oil. The lower cal-
orific value of the virgin oil is likely due to the presence of carbon
and long-chain carbon compounds of lower calorific value in the oil
matrix.
The densities and viscosities of the pyrolysis oils were found to
be lower than those of the waste oil due to the cracking of heavy
hydrocarbons to lighter compounds. The densities of the pyrolysis
oils (757–773 kg/m3), except for that from the experiments con-
ducted at a N2 purge rate of 750 ml/min, are quite close to that
for gasoline, and it is also within the prescribed range of 720–
775 kg/m3 given in British Standard of Unleaded Petrol (BS EN
228:2008 [37]). The flash points of the pyrolysis oils were all found
to be lower than that of diesel but higher than that of gasoline;
similar findings have been reported by other workers [13,15,39].

Table 3
Fuel properties of the virgin oil (FO), the waste automotive engine oil (WO) and the pyrolysis oils.

FO WO Pyrolysis oil Gasoline Desired liquid fuelb

a a
N2 purge rate (ml/min) WO feed rate (kg/h)
100 250 750 0.4 1 2.5 5
Density, q (kg/m3) 879 858 757 770 784 770 771 773 773 767 720–850c
Flash point (°C) 215 197 <19 <19 <19 <19 <18 <18 <18 40 <55d
Kinematic viscosity at 40 °C (mm2/s) 85 52 6.6 6.2 6.1 6.2 6.3 6.5 6.9 0.7 1–4e
CV (MJ/kg)f 43.6 45.4 44.3 46.5 45.7 46.5 46.5 46.6 46.6 46.1 36–48g
Sulphur (wt.%) 2.3 0.8 0.02 0.02 0.03 0.02 0.02 0.03 0.03 0.1 60.1h
Oxygen (ppm) 2.3 2.1 0.1 0.1 0.5 0.1 0.1 0.2 0.2 0 62.5i
Carbon components C21–C45 C11–C40 C5–C30 C5–C30 C5–C30 C5–C30 C5–C30 C5–C30 C5–C30 C5–C10 C5–C20j
(1 wt.% (5 wt.% (18 wt.% (5 wt.% (6 wt.% (9 wt.% (14 wt.%
C21–C30) C21–C30) C21–C30) C21–C30) C21–C30) C21–C30) C21–C30)
Solid content (wt.%) <0.1 <3k <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 –
Energy density (%)l – – 100 100 100 100 99 97 93 – –
3 months 6 months 9 months
Viscosity of pyrolysis oil over time (mm2/s)m 6.4 6.5 6.5
a
Process conditions: Pyrolysis at a constant WO feed rate of 0.4 kg/h was used when the effects of varying the N2 purge rate were studied, whereas a constant N2 purge rate
of 250 ml/min was used to study the effects of varying the WO feed rate, and all experiments were performed at a constant temperature of 550 °C.
b
Exhibiting desirable properties comparable to commercial liquid fuels derived from fossil fuel (e.g. diesel, kerosene, gasoline).
c
The density for gasoline: 720–775 kg/m3 [37,39,49], diesel: 820–860 kg/m3 [39].
d
The flash point for gasoline: 43 °C [13]; diesel:>55 °C [39,45].
e
The viscosity for unleaded gasoline: 0.7 mm2/s; diesel: 2–4 mm2/s [40].
f
CV – Calorific value, also regarded as higher heating value (HHV) in literature.
g
The calorific value (MJ/kg) of fossil fuels reported in literature: 43–46 for diesel [6,39,46], 43–48 for gasoline [13,39], 36–47 for kerosene [42,50].
h
The sulphur content for motor fuels reported in internationally prescribed standards:60.1 wt.% [36–38].
i
The oxygen content for gasoline and diesel: 0 wt.% [51], reformulated gasoline (RFG): 2 wt.% [52].
j
The carbon components of fossil fuels: C5–C20 (see Table 4).
k
Before filtration.
l
Energy density (%) in the pyrolysis oil was calculated based on the density and calorific value of gasoline, i.e. qPO * CVPO * 100/qgasoline * CVgasoline; PO – pyrolysis oil.
m
Data are presented for pyrolysis oil obtained with 1 kg/h of WO feed rate and 250 ml/min of N2 purge rate due to its closest gasoline-like composition and fuel properties.
336 S.S. Lam et al. / Fuel 92 (2012) 327–339
The low flash points suggest that the un-refined pyrolysis oils con-
tain components that have a lower boiling point range than diesel.
The pyrolysis oils possess slightly higher kinematic viscosities (6–
7 mm2/s) than diesel (2–4 mm2/s) [40], but are considerably higher
than that of gasoline (0.7 mm2/s). Further treatment may be
needed to reduce the viscosity of the pyrolysis oil to a value com-
parable to gasoline (<1 mm2/s) since a lower viscosity is desirable
and represents a favourable feature when it comes to handling and
transportation. Fig. 7 demonstrates that nearly 10% of the pyrolysis
oil shows a higher boiling range than that of diesel. This indicates
that the pyrolysis oil contains certain heavier hydrocarbon frac-
tions (i.e. higher boiling point components) that those of diesel.
These heavier fragments of long chain hydrocarbon components
may have contributed to the observation that the pyrolysis oil
has a higher viscosity than diesel.
The pyrolysis oils contain minor quantities of particulates
(<0.001 wt.%) present in the micrometer range (62 lm in size as
determined by Scanning-Electron-Microscopy). The particulates
are likely to derive from the very fine carbon particles originally
present in the pyrolysis reactor and chars generated during the
pyrolysis that escaped through the 0.45 lm ME25-filter fitted after
Fig. 7. Simulated distillation plot showing the boiling point distribution for
pyrolysis oil obtained in relation to different N2 purge rate (ml/min) and waste
oil feed rate (kg/h) (above) and compared to commercial liquid fuels (bottom).
the reactor. These particulates are likely to arise from agglomera-
tion of these smaller particles, which can be removed by filtration.
The calorific value of a fuel is another important fuel property
that indicates the gross energy output of combustion in the engine
chamber. The calorific value of the pyrolysis oils (46–47 MJ/kg), ex-
cept for the experiments conducted at 100 ml/min of N2 purge rate,
was higher than those of waste oil and close to those of traditional
liquid fuels derived from fossil fuel (43–48 MJ/kg), indicating that
pyrolysis oils with high combustion energy can be obtained by
microwave-heated pyrolysis. In particular, the pyrolysis oil ob-
tained with 1 kg/h of waste oil feed rate and 250 ml/min of N2
purge rate shows the closest calorific value to that of gasoline, rep-
resenting an ideal process condition to obtain gasoline-like fuel.
The decrease in oxygen content compared to the original waste
oil (Table 2, see Section 3.4) is likely to contribute to the increase
in the calorific value of the pyrolysis oils. In addition, a decrease
in H/C ratio (Table 2) was observed for pyrolysis oils compared
to the waste oil, suggesting that more carbon–carbon bonds were
formed in the pyrolysis oil, thus producing more energy during
combustion and showing a higher calorific value. The lower calo-
rific value of the waste oil is likely due to the presence of carbon
and long-chain carbon compounds of lower calorific value in the
oil matrix. The volumetric energy density of the pyrolysis oils
was found to be 93–100% of that of gasoline.
Overall, the process parameters (N2 purge rate and waste oil
feed rate) seemed to have little influence on the fuel properties
of the pyrolysis oils, suggesting that the microwave-heated pyroly-
sis may be a convenient way of recycling high volume of waste oil
into a useful oil product. Taking into account results from previous
work [5], for the particular configuration of the microwave pyroly-
sis system used in our apparatus, a pyrolysis temperature of 550 °C
coupled with 1 kg/h of waste oil feed rate and 250 ml/min of N2
purge rate provides the optimum balance between high process
yield while producing an oil product with fuel properties compara-
ble to gasoline, thereby reflecting its potential to generate a valu-
able liquid fuel. In addition, the pyrolysis oil produced from
these process conditions was checked for variations in viscosity
over a time period of 9 months, and showed negligible change over
this period and thus the pyrolysis oils exhibit good stability char-
acteristics (Table 3).
3.6.1. Boiling point distributions
To further examine the fuel properties of the pyrolysis oils,
ASTM D2887-08 and ASTM D3710-95(2009) standard simulated
distillations were performed on the pyrolysis oils and some of
the commercial liquid fuels derived from fossil fuel (i.e. diesel, ker-
osene, and gasoline); ASTM D3710-95(2009) was used specifically
for the analysis of samples having a low boiling point range (i.e.
gasoline). The boiling point ranges obtained for the various oils
were then plotted against the cumulative volume fractions of the
components of the oil, and these are presented in Fig. 7.
Fig. 7 outlines the effect of N2 purge rate and waste oil feed rate
on the boiling point distribution of the pyrolysis oils; the boiling
point curves plotted show the simulated distillation curves of the
various oils. The pyrolysis oils show a wide and much lower boiling
point range than that of waste oil, indicating the high extent of
thermal cracking incurred by the waste oil in microwave-heated
pyrolysis (see Section 3.3). The wide boiling point range is desir-
able as vaporisation at a narrow boiling point band could cause
immediate fuel burning in the engine combustion chamber, lead-
ing to high rates of pressure and temperature increase that could
damage the engine components. The wide and gradually increasing
boiling point curve shown by the pyrolysis oil promotes partial
vaporisation and combustion of fuels which are important for opti-
mal performance and safe operation in the engine [41]. There was
very little difference between the oils produced with different N2
 S.S. Lam et al. / Fuel 92 (2012) 327–339
purge rates and waste oil feed rates. However, at lower N2 purge
and waste oil feed rates, the pyrolysis oils were found to have high-
er amounts of lighter fractions with low boiling points. Decreasing
these two process parameters results in an increase in formation of
light hydrocarbons, which are likely to derive from enhanced
cracking of heavier hydrocarbons (i.e. higher boiling point compo-
nents) into smaller molecules due to longer residence times in-
curred by the pyrolysis volatiles in the reactor.
Fig. 7 also compares the boiling point distributions of hydrocar-
bons in the pyrolysis oil to those of commercial liquid fuels. Data
are presented for pyrolysis oil obtained with 1 kg/h of waste oil
feed rate and 250 ml/min of N2 purge rate as those conditions pro-
duce the highest yield of pyrolysis oils that are closely matched to
commercial fuels, particularly gasoline (see Section 3.6). Nearly
80% of the pyrolysis oil was found to fall below the boiling point
of diesel and kerosene. The recovered oil had a lower initial boiling
point and contained lighter fractions than those of diesel; similar
findings were reported by other researchers working on other
studies of waste oil pyrolysis [6,15].
For comparison purposes, the boiling point range obtained for
the pyrolysis oil was categorised into four petroleum fractions:
gasoline, kerosene, diesel, and heavy oil (>C19); the petroleum frac-
tions are defined based on the major carbon components and their
corresponding boiling point ranges detected in the various oils. Ta-
ble 4 compares the petroleum fractions in the pyrolysis oils pro-
duced from microwave-heated pyrolysis to those that are
obtained by pyrolysis using conventional electric heating. The
microwave-heated pyrolysis method generates an oil product
comprising mainly of compounds that are similar to gasoline
(70%) and some heavier components found in the kerosene
(16%) and diesel (17%). In addition, the results also reveal that
the waste oil, containing C11–C40 hydrocarbons, was thermally
cracked to mainly C4–C19 hydrocarbons, which were then con-
densed as pyrolysis oil, in which nearly 96% of the compounds
were within the C4–C19 range. It is likely that a significant portion
of the pyrolysis oil was obtained through pyrolysis cracking rather
than from the evaporation of the waste oil, since the pyrolysis oil
contains only 4% of long chain hydrocarbon components (>C19)
typical of the compounds in the original waste oil (Table 4). Over-
all, the pyrolysis oil demonstrates a boiling point range quite com-
parable to commercial liquid fuels, particularly gasoline,
suggesting that the oils could potentially be further processed to
transport-grade fuels.
The pyrolysis oil produced from microwave-heated pyrolysis
showed higher amounts of light fractions (C4–C19) compared with
those obtained from the oils pyrolysed by conventional electric
heating (Table 4). In addition, the examination of the hydrocarbon
Table 4
Comparison of petroleum fraction (%)a in the pyrolysis oil between pyrolysis driven
by microwave heating and conventional electric-resistance heatingb.
Type of waste oil pyrolysis Gasoline Kerosene Diesel
C4–C12 C11–C15 C15–C19
40– 175– 251–
190 °C 246 °C 342 °C
Microwave-heated pyrolysis 69 16 15
(this study)
Pyrolysis heated by electric 2.5–38 1 7–14
furnace [6]
Pyrolysis heated by electric 40 18 13
oven [15]
a
The petroleum fractions are categorised based on the major carbon components
and their corresponding boiling point ranges detected in the various oils.
b
The data from literature were estimated from the boiling point curve of waste
oil obtained in their waste oil pyrolysis studies.
337
composition of the oils (Table 1) revealed that waste oil was ther-
mally cracked to mainly 6C20 hydrocarbons compared to the 6C35
hydrocarbons produced in conventional electric-heated pyrolysis
[42]. These results suggest that cracking reactions are enhanced
in microwave-heated pyrolysis. The use of microwave heating as
a heat source shows improved efficiency in cracking the waste
oil to a desirable lighter fraction, comprising components (e.g.
C4–C12 hydrocarbons) within the range of commercial liquid fuels
whilst also showing a significantly greater yield of pyrolysis oil
(Fig 4, see Section 3.1). Possible explanations accounting for this
difference include the use of the microwave-heated carbon bed
in our set-up (in which the added waste oil becomes totally im-
mersed, providing excellent heat transfer, and also acts as a reduc-
ing reaction environment), and the microwave heating process
itself, which has been shown to produce different products from
conventional heating when all other factors are held equal
[10,24,43]. Mechanisms underlying this difference include possi-
bilities such as different heat distributions. Microwave heating vol-
ume heats only the carbon, creating a localised reaction hot zone as
opposed to electric heating which is externally applied and heats
all substances in the reactor volume including the surrounding
gas. Additionally, the creation of free elections on the surface of
the carbon particles as a result of microwave-induction may influ-
ence the reaction pathway. The proposed mechanisms are cur-
rently under investigation to further verify the explanations
postulated above. Pyrolysis using conventional electric heating
[6,15] was found to contain a higher amount (34–53%) of heavy
oil components (>C19), compared to only 4% observed in this study
(Table 4). We postulate that a significant portion of the heavy oil
fraction in pyrolysis oils is derived from distillation or evaporation
that occurs during the heating of waste oil. These processes trans-
fer hydrocarbons from both the uncracked and ‘less-cracked’ frac-
tions of waste oil in the reactor to the condensation system and
thus into the recovered pyrolysis oil. Evaporation has also been ob-
served in several pyrolysis studies of waste oil [9,14].
3.7. Energy recovery
Table 5 shows estimates of the energy recovery in the pyrolytic
products compared with the electrical energy consumption in the
microwave pyrolysis process. These estimates provide a useful
measure of the energy efficiency of the process. It should be men-
tioned that the calculations are limited by the following
assumptions:
1. Electrical consumption is based on the electrical power input
(7.5 kW) during the pyrolysis treatment, which is estimated to
be approximately 1.5 times the nominal output of the 4 magne-
trons (5 kW) for the sum of the periods when they are switched
on during the application of waste oil. However, it should be
noted that the 7.5 kW of electrical power input is an overesti-
mate of the actual electrical consumption, considering the
crude set-up of the prototype reactor and the fact that the
Heavy
oil
actual amount of absorbed power is not measured in this appli-
>C19 cation. Inclusion of a device in the set-up to log the forward and
>342 °C reflected power would optimise both the absorbed power and
the control over the process, increasing the viability to scale
4 up the process.
2. Heat losses from the prototype reactor are substantial and
53
would not be representative of the losses that would occur at
34
pilot or industrial scale. No attempt has been made to recover
energy during the cooling of the products in the condensation
system nor to fully insulate the reaction vessel and associated
fittings.
3. Pilot or industrial scale operation would involve the continuous
addition of waste oil without the need to repetitively heat the
338 S.S. Lam et al. / Fuel 92 (2012) 327–339

Table 5
Energy recovery and consumption in microwave-heated pyrolysis of waste automotive engine oil (WO).

Process conditions EWOa (kJ/h) EPOb (kJ/h) Erecoveryc (%) Epyrolysisd (kJ/h) Epyrolysise/EWO (%) Eratiof Ebalanceg (kJ/h)
h
WO feed rate
0.4 kg/h 18,160 15,624 86 6480 36 2 9144
1.0 kg/h 45,400 39,525 87 12,960 29 3 26,565
2.5 kg/h 113,500 100,190 88 20,250 18 5 79,940
5.0 kg/h 227,000 205,040 90 25,650 11 8 179,390
N2 purge rateh
100 ml/min 18,160 12,758 70 4320 24 3 8438
250 ml/min 18,160 15,624 86 6480 36 2 9144
750 ml/min 18,160 12,248 67 7560 42 2 4688
a
Estimated calorific value of the waste oil based on the CV and the different feeding rates of the WO (Table 4), i.e. CV of WO * WO feed rate.
b
Estimated calorific value of the pyrolysis oil (PO) based on the different CVs (Table 3) and wt.% yields (Fig. 2) of the pyrolysis oil, and the different feeding rates of the WO,
i.e. CV of pyrolysis oil * wt.% yield of pyrolysis oil * WO feed rate/100.
c
Energy recovery (%) in the pyrolysis oil was calculated based on the energy recovered from the waste oil, i.e. EPO * 100/EWO.
d
Electrical energy consumed during the pyrolysis treatment of the added WO sample (estimated during the time the WO sample started to be/was added to the reactor
until feeding was stopped after 2 h of operation); electrical power input – 7.5 kW, i.e. 1.5 * 5 kW of nominal output of 4 magnetrons.
e
Amount of energy (from EWO) consumed by Epyrolysis.
f
Energy ratio, defined as the energy content of the pyrolysis oil divided by the electrical energy input needed to operate the system, i.e. EPO/Epyrolysis.
g
Energy balance, defined as the energy content of the pyrolysis oil minus the electrical energy input needed to operate the system, i.e. EPO Epyrolysis.
h
Process conditions: Pyrolysis at a constant WO feed rate of 0.4 kg/h was used when the effects of varying the N2 purge rate were studied, whereas a constant N2 purge rate
of 250 ml/min was used to study the effects of varying the WO feed rate, and all experiments were performed at a constant temperature of 550 °C.

apparatus from room temperature. Calculations that include the
electrical energy used to heat the reactor to the desired process
temperature will seriously overestimate the actual electrical
consumption during pilot or industrial scale, hence, this energy
expenditure is excluded from the energy calculations shown in
Table 5.
4. The calorific value of the non-condensable pyrolysis products is
ignored.
The pyrolysis oils showed significantly high recovery of the en-
ergy content of the waste oil, ranging between 67% and 90%. The
electrical energy (Epyrolysis) supplied to power the microwave-
heated pyrolysis process ranged from 11% to 42% of the calorific
value of the waste oil pyrolysed (Epyrolysis/EWO) over the range of
purge and feed rates considered. The results also show that more
electrical energy (Epyrolysis) was needed to pyrolyze the waste oil
at higher feed rates, as a direct result of the need for more energy
to heat higher quantities of waste oil to the operational tempera-
ture and to supply the endothermic enthalpy to drive the higher
amount of pyrolysis reactions. The higher relative electrical energy
usage (Epyrolysis/EWO) observed at lower waste oil feed rates indi-
cates that a the process is less energy efficient when pyrolysis is
conducted at lower feed rates, probably as a result of a greater
influence of heat loss from the reactor under these conditions.
On the other hand, the higher energy consumption observed at
higher N2 purge rates suggested that additional electrical energy
was needed to overcome the cooling effects that resulted from
the higher N2 purge rates.
Even given the limitations involved in estimating energy con-
sumption in the laboratory scale equipment described above, it is
clear that the process is capable of recovering a hydrocarbon prod-
uct (pyrolysis oil) whose calorific value is many times greater than
the amount of electrical energy used in the operation of the pro-
cess, as indicated by energy ratios ranging between 2 and 8 (Ta-
ble 5). This favourable situation would be even more apparent
during the operation of pilot or industrial scale equipment in
which attempts to improve heat integration and recovery have
been implemented. These results suggest that a reactor heated
by a magnetron system with a total electrical power input of
7.5 kW is capable of processing waste oil at a flow rate of 5 kg/h,
producing liquid pyrolysis products with an energy content
equivalent to approximately 60 kW. The calorific value of the
non-condensable pyrolysis products has been ignored in this
assessment. Inclusion of the energy content of this stream would
further increase the amount of energy that can be recovered from
waste oil. This gaseous stream could be used for on-site generation
of electrical energy to power the magnetron system.
However, it should be noted that the high energy recovery ra-
tios observed in this study involve the assumption that the only
energy input of the process is the electrical energy used in the
pyrolysis reactor. In practice lower energy ratios should be consid-
ered in which higher energy inputs should be taken into account,
including the energy needed for the collection and transport of
waste oil to the processing plant, and for the refining of the pyro-
lysis oils if they are needed to be further processed to produce a
commercial gasoline fuel (e.g. the conversion of both the aromatic
and the heavy hydrocarbon components into gasoline type compo-
nents). Overall, the results show that the microwave-heated pyro-
lysis method may be a viable means of recycling the waste oil into
a useful oil product, in addition to a disposal method for the waste
oil.
4. Conclusion
N2 purge rate and waste oil feed rate, in addition to the use of a
microwave heated bed of particulate carbon, were found to have
effects on the fraction of original waste oil converted to pyrolysis
gases, pyrolysis oils, and char residues. These process parameters
also influenced the concentrations and molecular nature of the dif-
ferent hydrocarbons formed in the pyrolysis oils. These results, in
combination with results from previous work [5], demonstrate that
microwave-heated pyrolysis generated an 88 wt.% yield of gaso-
line-like oil product that contains potentially valuable light ali-
phatic and aromatic hydrocarbons. The oil product is also
relatively contaminant free with low levels of sulphur, oxygen,
and toxic PAH compounds, and is almost entirely free of metals
as reported in previous work [5], thereby reflecting its potential
as a green energy source or chemical feedstock. The pyrolysis oil
could potentially be treated and upgraded to transport grade fuels,
or added to petroleum refinery as a chemical feedstock for further
processing, although further studies are needed to confirm these
possibilities. The microwave-heated pyrolysis can be performed
in a continuous operation to treat high volumes of waste oil while
showing both a positive energy ratio and a high net energy output.
It is clear that microwave-heated pyrolysis offers an exciting green
approach to the treatment and recycling of automotive lubricating
 S.S. Lam et al. / Fuel 92 (2012) 327–339
oil. This unique combination of properties enables the potential
generation of products with significant commercial value out of
what would otherwise be a toxic and difficult to dispose of chem-
ical liability.
Acknowledgements
Su Shiung Lam acknowledges the financial assistance by Public-
Service-Department of Malaysia Government and University
Malaysia Terengganu.
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