This article appeared in a journal published by Elsevier.

The attached
copy is furnished to the author for internal non-commercial research
and education use, including for instruction at the authors institution
and sharing with colleagues.
Other uses, including reproduction and distribution, or selling or
licensing copies, or posting to personal, institutional or third party
websites are prohibited.
In most cases authors are permitted to post their version of the
article (e.g. in Word or Tex form) to their personal website or
institutional repository. Authors requiring further information
regarding Elseviers archiving and manuscript policies are
encouraged to visit:
http://www.elsevier.com/copyright

Author's personal copy

Fuel 92 (2012) 327339

Contents lists available at ScienceDirect

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

Microwave-heated pyrolysis of waste automotive engine oil: Inuence

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
b
c

Department of Chemical Engineering and Biotechnology, University of Cambridge, New Museums Site, Pembroke Street, Cambridge CB2 3RA, United Kingdom
BP Institute, Bullard Laboratories, University of Cambridge, Madingley Road, Cambridge CB3 0EZ, United Kingdom
Department of Engineering Science, University Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia

a r t i c l e

i n f o

Article history:
Received 17 May 2011
Received in revised form 11 July 2011
Accepted 13 July 2011
Available online 28 July 2011
Keywords:
Pyrolysis
Microwave pyrolysis
Waste oil
Pyrolysis oil
Fuel

a b s t r a c t
The pyrolysis of waste automotive engine oil was investigated using microwave energy as the heat
source, and the yield and characteristics of the pyrolysis oils (i.e. elemental analysis, hydrocarbon composition, and potential fuel properties) are presented and discussed. The microwave-heated pyrolysis
generated an 88 wt.% yield of condensable pyrolysis oil with fuel properties (e.g. density, caloric value)
comparable to traditional liquid transportation fuels derived from fossil fuel. Examination of the composition of the oils showed the formation of light aliphatic and aromatic hydrocarbons that could also be
used as a chemical feedstock. The oil product showed signicantly high recovery (90%) of the energy present in the waste oil, and is also relatively contaminant free with low levels of sulphur, oxygen, and toxic
PAH compounds. The high yield of pyrolysis oil can be attributed to the unique heating mode and chemical environment present during microwave-heated pyrolysis. This study extends existing ndings on the
effects of pyrolysis process conditions on the overall yield and formation of the recovered oils, by demonstrating that feed injection rate, ow rate of purge-gas, and heating source inuence the concentration
and the molecular nature of the different hydrocarbons formed in the pyrolysis oils. The microwaveheated pyrolysis can be performed in a continuous operation, and the apparatus described which is tted
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 microwave-heated pyrolysis shows exceptional promise as a means for recycling and treating problematic
waste oil.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
The production of waste automotive engine oil is estimated at
24 million tons each year throughout the world, posing a signicant treatment and disposal problem for modern society. The
waste oil, containing a mixture of aliphatic and aromatic hydrocarbons, also represents a potential source of high-value fuel and
chemical feedstock. The preferred disposal options in most countries are incineration and combustion for energy recovery, and vacuum distillation and hydro-treatment for re-rening 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 Biotechnology, 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).
0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.07.027

concerns over environmental pollution, and the difculties and

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 [46] the waste material is thermally cracked and decomposed 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 renery
feedstocks for further processing [7]. Most of the literature reports
focus on pyrolysis using conventional electric resistance and electric 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

Author's personal copy

328

S.S. Lam et al. / Fuel 92 (2012) 327339

have been elaborated in previous work [5] and will not be duplicated here. In this process, waste oil is mixed with highly microwave-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 different composition depending on the reaction conditions. The use
of microwave radiation as a heat source is known to offer additional 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 reected by the increasing amount of research reported in the literature [7,11,12]. Microwave radiation
provides a rapid and energy-efcient heating process compared
to conventional technologies. The diffuse nature of the electromagnetic eld allows microwave heating to evenly heat many substances 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 heating rates, facilitating increased production speeds and decreased
production costs. Furthermore, energy is targeted only to microwave 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 prole and improved yield of desirable products. The process is physically gentle, allowing for a wide variety of
applications in diverse elds.
This study investigates the inuence of process parameters
(feed injection rate, purge gas ow, and heating source) on the
yield and characteristics of the pyrolysis oils produced from microwave-heated pyrolysis of the waste oil, with a focus on their elemental 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 information is available concerning the inuence of key process parameters on the pyrolysis of waste oil, although a few studies have
been performed on electric resistance heated pyrolysis of waste
oil [6,1315].

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., Bodio, Switzerland) used as microwave absorbent to heat the waste oil,
and their pre-experimental treatment have been reported in previous works [5,7]. Before pyrolysis, the waste oil samples were ltered 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 elemental analysis; caloric value was determined by bomb
calorimetry.
2.2. Experimental details
The experimental apparatus for this investigation has been described in detail in previous work [5]. The only change from this
description is the addition of a mixed-cellulose-ester membrane
lter (0.45 lm ME25 lter, 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 rened 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) lled 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 (250700 C), feed injection
rates (0.45 kg/h) and purge gas ows (0.10.75 L/min) to understand the inuence of these process parameters on the nal pyrolysis 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 throughout the reactor and to maximise heat transfer during pyrolysis. The
waste oil is nearly transparent to microwaves due to its non-polarity nature, therefore it requires heating by contact with microwave
absorbent materials (e.g. carbon-based materials such as particulate carbon) in order to achieve pyrolytic thermal cracking. The

Fig. 1. Schematic layout of microwave-heated pyrolysis system.

Author's personal copy

S.S. Lam et al. / Fuel 92 (2012) 327339

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 generate sufcient heat to maintain the desired target temperature at
all these ow 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 vapour 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 liquid 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-lter 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 collecting vessels and lter. 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 recorded is the average of the results obtained from three valid repeated runs performed under identical conditions. These runs
showed good reproducibility and precision with low standard
deviations shown in the product yield (15 wt.%). The virgin oil
(FO), the waste oil, and the pyrolysis oils were examined for hydrocarbon composition by gas chromatography coupled with a mass
selective spectrometry detector (GCMS) and a ame 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. caloric value, density, ash point, viscosity, boiling point distribution) 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 monitored 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 addition, 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 difcult during the heating process rstly,
there are inherent difculties involved in measuring this parameter 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 distribution, 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 equilibration and steady state temperature were reached, the temperature 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 GCMS instrument (Agilent Technologies, Palo Alto, CA), allowing the quantication of compounds by both species and size; compounds were
identied using the NIST 2005 mass spectral library using similarity indices of >70%, or by comparison with published GCMS data
for similar products; the detailed description of this analytical
method have been reported in previous work [7] For polycyclic
aromatic hydrocarbons (PAHs), the GCMS instrument was programmed into selected-ion-monitoring (SIM) mode and the peaks
were compared to external PAH standards for quantication. In
addition to GCMS analysis, the oils were analysed by the 6890
gas chromatograph coupled with a ame ionisation detector, using
a 30 m HP-5 capillary column (5% phenyl methyl silicone, I.D.
0.53 mm, lm 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 nal holding time of 30 min. Quantication of compounds on the
GC-FID was obtained by external standard method and relative
retention times once the component has been identied by the
GCMS analysis. The data obtained from GC-FID were used to evaluate 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 owing 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 VTF900 pyrolysis furnace (LECO Corporation, Michigan, USA). The oxygen 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 generated 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, Germany) 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 ash 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 sample 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 ow rate of 0.1 L/min.
Oil samples were also analysed for caloric value using a Parr
6200 Isoperibol bomb calorimeter (Parr Instrument, Moline, Illinois). Detailed analysis and sample preparation were performed
according to ASTM Standard D4809-09a. [22] The solid content
(ethanol-insoluble) was determined by ltering the pyrolysis oil
through a 0.1-lm polycarbonate membrane lter (Milipore Co.,

Author's personal copy

330

S.S. Lam et al. / Fuel 92 (2012) 327339

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

after ltration.
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 products, with a special emphasis on the pyrolysis oil. The main objective was to convert the waste oil to petrochemical products
suitable for use as a fuel or raw chemical feedstock. This paper explored the effects of varying the feed injection rate of waste oil, and
the purge gas ow 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 pyrolysis 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 increase in waste oil feed rate demonstrated a minor inuence on
the yield of pyrolysis oil, as the total increase in the yield of pyrolysis 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 ow
of pyrolysis volatiles out of the reaction hot zone inside the reactor. It is also believed that the higher rates of N2 purge gas resulted
in a more rapid ow 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 conditions; similar ndings were reported by other workers [23]. At very
high N2 purge rates (750 ml/min), the yield of pyrolysis oil decreases, suggesting that the installed condensation system is unable to condense the pyrolysis volatiles at this considerably
faster vapour ow 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 pyrolysis 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, dened 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 pyrolysis reactor is able to process each hour a waste oil feed up to ve
times the mass of the particulate carbon while maintaining a relatively high production of pyrolysis oil from the feed (8588 wt.%).
The use of a microwave-heated bed of particulate carbon in this
set-up showed good heat transfer and cracking capacity to pyrolyse 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

Author's personal copy

S.S. Lam et al. / Fuel 92 (2012) 327339

Fig. 3. The yields (wt.%) of pyrolysis oil in relation to weight hourly space velocity
(h 1).

bed in order for pyrolysis to occur [5]. Overall, the waste oil feed
rate was found to have little inuence on the yields of pyrolysis
product (Fig. 2), indicating the potential of this pyrolysis process
in treating high volumes of waste oil while maintaining a relatively
high throughput of pyrolysis oil (Fig. 3).
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
(Fig. 2). It is assumed that this represents the optimum balance between sufciently high purge and feed rates to sweep the evolved
pyrolysis volatiles out of the reactor, thus producing condensable
vapours (pyrolysis oil) by avoiding the promotion of secondary
reactions that would result in increased formation of incondensable gases and char residues, while not being so high that the condensation system was unable to condense the pyrolysis volatiles. It
should be noted that 5 kg/h is the highest waste oil feed rate that
can be processed in this experimental device as it was ascertained
that the 5 kW magnetron system of the microwave oven could no
longer generate sufcient heat to maintain the desired operating
temperature (550 C) at ow rates of 6 kg/h and above. Our results
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 processes 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, compared to the other methods of operation, seemed to have a benecial 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 applied 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 volatiles 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 differences between conventional and microwave pyrolysis have also

331

Fig. 4. Comparison of oil yield in waste oil pyrolysis processes heated with different
media (waste oil only [6,8,13,4446], coal [47,48], scrap tires [15]), and by different
heating system (microwave heating, conventional electric heating).

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

26]. These results suggest that the pyrolysis of waste oil is inuenced by the heating system (heating source, heating media) in
addition to the other factors commonly reported in literature
(e.g. feed composition and ow rate, catalyst, temperature,
pressure).
3.2. Visual inspection of pyrolysis operation
The conversion of waste oil to pyrolysis oil started to occur
when the operating temperature was above 400 C, where over
50 wt.% of the product was a viscous oil mixture. The maximum
conversion of waste oil was accomplished at 550 C, during which
P67 wt.% of the waste oil was transformed into pyrolysis oil
(Fig. 2). The pyrolysis oil obtained at 550 C was a fairly pale yellowish-gold hydrocarbon liquid (Fig. 5) containing a small amount
of dark solids. It is thought that these solids derived from the small
quantities of very ne carbon particles originally present in the
pyrolysis reactor; these are likely to escape from the reactor and
co-migrate with the pyrolysis oil. These particles can be removed

Fig. 5. Pyrolysis oil from microwave pyrolysis of waste oil.

Author's personal copy

332

S.S. Lam et al. / Fuel 92 (2012) 327339

by ltration. 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
GCMS 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 hydrocarbon compounds were in the C21C45 range for virgin oil, but
only C11C40 were detected in waste oil (Table 1). This concurs
with previous ndings [5,7] that suggest the conversion of a fraction 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. naphthenes (cycloalkanes), alkanes, alkenes, aromatics, and unknowns
(unidentied 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 C11C40 hydrocarbons, was thermally cracked to oil products comprising mainly

of C5C30 hydrocarbons, and which were dominated by aliphatic

hydrocarbons (5071 wt.%) and signicant amounts of aromatics
(2342 wt.%). This indicates the occurrence of cracking of compounds to produce some aromatic structures, possibly derived
from cyclisation and aromatisation reactions that occurred during
pyrolysis. The aliphatic hydrocarbons were mostly alkanes (3147
wt.%), and alkanes from pentane to decane were present at the
highest concentrations. Alkenes (923 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 C5C20 aliphatic fractions, represent a potentially
high-value chemical feedstock or fuel source. The alkanes could
be upgraded to produce transport-grade fuels, or gasied to commercially valuable gaseous products including hydrogen, whereas
the alkenes are highly desired feedstocks in petrochemical industry, 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 follows the free-radical-induced random scission mechanism [27
30]. This mechanism may have led to the production of hydrocarbon 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

2.5

91
0.5
0.5

31.4
10.2
8.6

39.6
7.6
17.7

47
1.4
22.6

39.6
7.6
17.7

40.4
6.5
18.2

42
5.7
18.8

43.9
3.9
20.1

91

92

50.2

64.9

71

64.9

65.1

66.5

67.9

60
29
2

3
7
57
25

29
13.2
7
1

32
15
13.3
4.6

20.4
14.3
18.2
18.1

32
15
13.3
4.6

29.2
14.8
15.2
5.9

24.4
14.9
17.9
9.3

21.5
13.4
18.8
14.2

Aromatics
Benzene (C6H6)
Toluene (C7H8
Xylene (C8H10)
Alkylbenzenesd

0.5

1.1

11.8
11.9
9.4
8.4

6.6
7.8
7.1
8.2

2.1
2.3
3.6
14.6

6.6
7.8
7.1
8.2

4.5
5.6
6.2
12.8

4.1
4.7
5.4
13.1

3.5
3.4
4.7
13.9

Total

0.5

1.1

41.5

29.7

22.6

29.7

29.1

27.3

25.5

PAHs
Naphthalene
Acenaphthene
Acenaphthylene
Phenanthrene
Anthracene
Pyrene

0.03

0.003

0.002

0.1

0.01

0.02

0.41
0.09
0.08
0.07
0.16
0.09

0.23
0.03
0.04
0.04
0.11
0.05

0.13
0.02
0.02

0.03

0.23
0.03
0.04
0.04
0.11
0.05

0.17
0.02
0.02
0.03
0.06

0.10
0.02
0.02
0.01
0.05

0.12
0.02
0.02
0.01
0.03

Aliphatics
Alkanes
Naphthenes (Cycloalkanes)
Alkenesb

89.7
0.5
0.8

Total
Carbon components
C5C10
C11C15
C16C20
C21C30
C31C40
C41C45

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 unidentied peaks.

Author's personal copy

333

S.S. Lam et al. / Fuel 92 (2012) 327339

then cracked to form lighter compounds. This accounts for the alkanes, naphthenes, and alkenes observed for each carbon number
across all collected samples.
Valuable light aromatics such as BTX (the sum of benzene, toluene, and xylene) were found in signicant quantities (833 wt.%)
in the pyrolysis oils. The aromatics were composed mainly of single ring alkyl aromatics, including benzene derivatives such as 1,3diethylbenzene, 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 nonbranched saturated compounds. Polycyclic aromatic compounds
(PAHs) were observed in the pyrolysis oil but only in minor quantities (60.9 wt.%). Several sulphur and/or nitrogen-containing compounds 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 aliphatic and aromatic content improved towards smaller hydrocarbon chains. The amounts of alkanes and alkenes were reduced in
favour of aromatic formation (including PAHs). This agrees with
the ndings in previous works [5,30,31], which propose that an increase 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 DielsAlder type secondary reactions, which involve 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 microwaveheated pyrolysis in a manner similar to that reported in other pyrolysis processes [25,34], since n-alkenes and dialkenes (e.g. 1.3butadiene) 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 DielsAlder 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 DielsAlder type reactions in pyrolysis 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 mechanism 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 occurrence 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 (C5C20) 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 ow of pyrolysis volatiles
out from the reactor led to decreased participation of pyrolysis volatiles (evolved from the waste oil compounds) in secondary reactions (e.g. secondary thermal cracking) and helps to explain the
greater quantities of heavier hydrocarbon components in the pyrolysis oil. Moreover, it is thought that most of the heavier components 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 produce valuable oil products with this microwave pyrolysis apparatus. The benet of pyrolysing waste oil at high feed rates to
increase the yield of total oil product is negated by the signicant
increase in the yield of undesirable heavier hydrocarbon components (>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 oxygen were detected in very low concentrations (62.1 wt.%). The carbon and hydrogen are mainly from the base oils from which the
lubricating oil is formulated, whereas nitrogen, sulphur and oxygen 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 oxides, which subsequently escape to the atmosphere during engine
operation.
The pyrolysis oils showed a much lower content of oxygen and
a signicantly 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

C
H
N
S
O
H/C (mol/mol)
H/O (mol/mol)
O/C (mol/mol)

82.7
12.5
0.1
2.3
2.3
1.8
86
0.02

81.7
15.1
0.1
0.8
2.1
2.2
114
0.02

WO feed rate (kg/h)a

100

250

750

0.4

2.5

88.6
11.2
0.1
0.02
0.1
1.5
1778
0.001

85.6
14.2
0.1
0.02
0.1
2.0
2254
0.001

85.7
13.7
0.1
0.03
0.5
1.9
435
0.004

85.6
14.2
0.1
0.02
0.1
2.0
2254
0.001

85.1
14.3
0.1
0.02
0.1
2.0
2270
0.001

84.9
14.5
0.1
0.03
0.2
2.0
1151
0.002

84.6
14.6
0.2
0.03
0.2
2.1
1159
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.

Author's personal copy

334

S.S. Lam et al. / Fuel 92 (2012) 327339

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 reactions of unsaturated compounds in the pyrolysis oil during storage,
generating larger molecules (e.g. tar or sludge from polymerisation
of olens) 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 reactions 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 previous works [5]. The reduction in oxygen content is also likely to be
due to decarboxylation commonly occurring during thermal treatment processes; this agrees with the ndings of Sinag 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 another 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 caloric 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 variations 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

containing carbon double-bonds (e.g. alkenes, aromatics) with a

lower H/C ratio; the result is consistent with the hydrocarbon composition and functional groups found by GCMS and FTIR analysis
(see Sections 3.3 and 3.5). The purge and feed rates seem to have
had only a minor inuence 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 oxygen during pyrolysis to form sulphur oxides. In addition, new sulphur compounds may be formed during pyrolysis, e.g. metal or
non-volatile inorganic sulphides [15,35], which remain in the carbon bed; these reactions lead to decreased sulphur content in the
pyrolysis-oils. In all cases the sulphur content of the pyrolysis oil
obtained (2030 ppm) was found to meet internationally prescribed 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 Regulations 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

Fig. 6. FTIR spectrum (above) and the functional groups (bottom) detected in pyrolysis oil.

Author's personal copy

335

S.S. Lam et al. / Fuel 92 (2012) 327339

molecular species), which can lead to increased oil viscosity and

causing problems such as lter plugging and system fouling. Overall, 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 analysis (see Table 2), and the benecial effects of the carbon bed (acting as a reducing reaction environment) in decreasing both the oil
oxidation and the resulting formation of undesired oxidised species (see Section 3.4).

treating this kind of problematic waste oils. The low sulphur and
oxygen content is benecial to upgrading the pyrolysis oil to transport-grade fuels.
3.5. FTIR analysis
Fig. 6 shows the infrared spectrum of the pyrolysis oil obtained
by FTIR analysis and the general classication of chemical compounds from the FTIR spectrum; the classication was dened
based on the degree of infrared absorption (or transmittance) detected 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 microwaveheated pyrolysis of waste oil as there was little difference in the
FTIR spectra obtained with the different process parameters (N2
purge ow and waste oil feed rate), except for a small variation
in the transmittance peak intensities detected at the different frequency 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 vibrations, 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 characteristic 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. Carboxylic acids, in particular, are undesirable as they are the common
cause of acidic corrosion and sludge formation (as a result of polymerisation in which carboxylic acids combine to form larger

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 collected from a local petrol station (Table 3). The waste oil shows a
lower density but higher caloric 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 caloric value of the virgin oil is likely due to the presence of carbon
and long-chain carbon compounds of lower caloric 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 (757773 kg/m3), except for that from the experiments conducted 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 ash points of the pyrolysis oils were all found
to be lower than that of diesel but higher than that of gasoline;
similar ndings 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
N2 purge rate (ml/min)

Density, q (kg/m3)
Flash point (C)
Kinematic viscosity at 40 C (mm2/s)
CV (MJ/kg)f
Sulphur (wt.%)
Oxygen (ppm)
Carbon components

879
215
85
43.6
2.3
2.3
C21C45

858
197
52
45.4
0.8
2.1
C11C40

Solid content (wt.%)

Energy density (%)l

<0.1

<3k

Viscosity of pyrolysis oil over time (mm2/s)m

a

b
c
d
e
f
g
h
i
j
k
l
m

Gasoline

Desired liquid fuelb

767
40
0.7
46.1
0.1
0
C5C10

720850c
<55d
14e
3648g
60.1h
62.5i
C5C20j

<0.001

WO feed rate (kg/h)

100

250

750

0.4

2.5

757
<19
6.6
44.3
0.02
0.1
C5C30
(1 wt.%
C21C30)
<0.001
100

770
<19
6.2
46.5
0.02
0.1
C5C30
(5 wt.%
C21C30)
<0.001
100

784
<19
6.1
45.7
0.03
0.5
C5C30
(18 wt.%
C21C30)
<0.001
100

770
<19
6.2
46.5
0.02
0.1
C5C30
(5 wt.%
C21C30)
<0.001
100

771
<18
6.3
46.5
0.02
0.1
C5C30
(6 wt.%
C21C30)
<0.001
99

773
<18
6.5
46.6
0.03
0.2
C5C30
(9 wt.%
C21C30)
<0.001
97

773
<18
6.9
46.6
0.03
0.2
C5C30
(14 wt.%
C21C30)
<0.001
93

3 months

6 months

9 months

6.4

6.5

6.5

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.
Exhibiting desirable properties comparable to commercial liquid fuels derived from fossil fuel (e.g. diesel, kerosene, gasoline).
The density for gasoline: 720775 kg/m3 [37,39,49], diesel: 820860 kg/m3 [39].
The ash point for gasoline: 43 C [13]; diesel:>55 C [39,45].
The viscosity for unleaded gasoline: 0.7 mm2/s; diesel: 24 mm2/s [40].
CV Caloric value, also regarded as higher heating value (HHV) in literature.
The caloric value (MJ/kg) of fossil fuels reported in literature: 4346 for diesel [6,39,46], 4348 for gasoline [13,39], 3647 for kerosene [42,50].
The sulphur content for motor fuels reported in internationally prescribed standards:60.1 wt.% [3638].
The oxygen content for gasoline and diesel: 0 wt.% [51], reformulated gasoline (RFG): 2 wt.% [52].
The carbon components of fossil fuels: C5C20 (see Table 4).
Before ltration.
Energy density (%) in the pyrolysis oil was calculated based on the density and caloric value of gasoline, i.e. qPO * CVPO * 100/qgasoline * CVgasoline; PO pyrolysis oil.
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.

Author's personal copy

336

S.S. Lam et al. / Fuel 92 (2012) 327339

The low ash points suggest that the un-rened pyrolysis oils contain components that have a lower boiling point range than diesel.
The pyrolysis oils possess slightly higher kinematic viscosities (6
7 mm2/s) than diesel (24 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 comparable 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 fractions (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 ne carbon particles originally
present in the pyrolysis reactor and chars generated during the
pyrolysis that escaped through the 0.45 lm ME25-lter tted 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 agglomeration of these smaller particles, which can be removed by ltration.
The caloric value of a fuel is another important fuel property
that indicates the gross energy output of combustion in the engine
chamber. The caloric value of the pyrolysis oils (4647 MJ/kg), except 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 (4348 MJ/kg), indicating that
pyrolysis oils with high combustion energy can be obtained by
microwave-heated pyrolysis. In particular, the pyrolysis oil obtained with 1 kg/h of waste oil feed rate and 250 ml/min of N2
purge rate shows the closest caloric value to that of gasoline, representing 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 caloric 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 carboncarbon bonds were
formed in the pyrolysis oil, thus producing more energy during
combustion and showing a higher caloric value. The lower caloric value of the waste oil is likely due to the presence of carbon
and long-chain carbon compounds of lower caloric value in the
oil matrix. The volumetric energy density of the pyrolysis oils
was found to be 93100% of that of gasoline.
Overall, the process parameters (N2 purge rate and waste oil
feed rate) seemed to have little inuence on the fuel properties
of the pyrolysis oils, suggesting that the microwave-heated pyrolysis 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 conguration of the microwave pyrolysis 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 comparable to gasoline, thereby reecting its potential to generate a valuable 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 characteristics (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, kerosene, and gasoline); ASTM D3710-95(2009) was used specically
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 desirable as vaporisation at a narrow boiling point band could cause
immediate fuel burning in the engine combustion chamber, leading 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 optimal performance and safe operation in the engine [41]. There was
very little difference between the oils produced with different N2

Author's personal copy

S.S. Lam et al. / Fuel 92 (2012) 327339

purge rates and waste oil feed rates. However, at lower N2 purge
and waste oil feed rates, the pyrolysis oils were found to have higher 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 components) into smaller molecules due to longer residence times incurred by the pyrolysis volatiles in the reactor.
Fig. 7 also compares the boiling point distributions of hydrocarbons 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 produce 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
ndings 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 fractions are dened based on the major carbon components and their
corresponding boiling point ranges detected in the various oils. Table 4 compares the petroleum fractions in the pyrolysis oils produced 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 C11C40 hydrocarbons, was thermally
cracked to mainly C4C19 hydrocarbons, which were then condensed as pyrolysis oil, in which nearly 96% of the compounds
were within the C4C19 range. It is likely that a signicant 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). Overall, the pyrolysis oil demonstrates a boiling point range quite comparable 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 (C4C19) 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

Microwave-heated pyrolysis
(this study)
Pyrolysis heated by electric
furnace [6]
Pyrolysis heated by electric
oven [15]

Gasoline

Kerosene

Diesel

C4C12
40
190 C

C11C15
175
246 C

C15C19
251
342 C

69

16

15

2.538
40

1
18

Heavy
oil
>C19
>342 C
4

714

53

13

34

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 thermally 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 efciency in cracking the waste
oil to a desirable lighter fraction, comprising components (e.g.
C4C12 hydrocarbons) within the range of commercial liquid fuels
whilst also showing a signicantly 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 immersed, providing excellent heat transfer, and also acts as a reducing 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 possibilities such as different heat distributions. Microwave heating volume 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 inuence the reaction pathway. The proposed mechanisms are currently under investigation to further verify the explanations
postulated above. Pyrolysis using conventional electric heating
[6,15] was found to contain a higher amount (3453%) of heavy
oil components (>C19), compared to only 4% observed in this study
(Table 4). We postulate that a signicant 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 transfer hydrocarbons from both the uncracked and less-cracked fractions of waste oil in the reactor to the condensation system and
thus into the recovered pyrolysis oil. Evaporation has also been observed 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 efciency of the process. It should be mentioned 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 magnetrons (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 overestimate of the actual electrical consumption, considering the
crude set-up of the prototype reactor and the fact that the
actual amount of absorbed power is not measured in this application. Inclusion of a device in the set-up to log the forward and
reected power would optimise both the absorbed power and
the control over the process, increasing the viability to scale
up the process.
2. Heat losses from the prototype reactor are substantial and
would not be representative of the losses that would occur at
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
ttings.
3. Pilot or industrial scale operation would involve the continuous
addition of waste oil without the need to repetitively heat the

Author's personal copy

338

S.S. Lam et al. / Fuel 92 (2012) 327339

Table 5
Energy recovery and consumption in microwave-heated pyrolysis of waste automotive engine oil (WO).
Process conditions
WO feed rate
0.4 kg/h
1.0 kg/h
2.5 kg/h
5.0 kg/h

N2 purge rateh
100 ml/min
250 ml/min
750 ml/min
a
b

c
d

e
f
g
h

EWOa (kJ/h)

EPOb (kJ/h)

Erecoveryc (%)

Epyrolysisd (kJ/h)

Epyrolysise/EWO (%)

Eratiof

Ebalanceg (kJ/h)

18,160
45,400
113,500
227,000

15,624
39,525
100,190
205,040

86
87
88
90

6480
12,960
20,250
25,650

36
29
18
11

2
3
5
8

9144
26,565
79,940
179,390

18,160
18,160
18,160

12,758
15,624
12,248

70
86
67

4320
6480
7560

24
36
42

3
2
2

8438
9144
4688

Estimated caloric 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.
Estimated caloric 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.
Energy recovery (%) in the pyrolysis oil was calculated based on the energy recovered from the waste oil, i.e. EPO * 100/EWO.
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.
Amount of energy (from EWO) consumed by Epyrolysis.
Energy ratio, dened as the energy content of the pyrolysis oil divided by the electrical energy input needed to operate the system, i.e. EPO/Epyrolysis.
Energy balance, dened as the energy content of the pyrolysis oil minus the electrical energy input needed to operate the system, i.e. EPO Epyrolysis.
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 caloric value of the non-condensable pyrolysis products is
ignored.
The pyrolysis oils showed signicantly high recovery of the energy content of the waste oil, ranging between 67% and 90%. The
electrical energy (Epyrolysis) supplied to power the microwaveheated pyrolysis process ranged from 11% to 42% of the caloric
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 temperature 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 indicates that a the process is less energy efcient when pyrolysis is
conducted at lower feed rates, probably as a result of a greater
inuence 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 consumption in the laboratory scale equipment described above, it is
clear that the process is capable of recovering a hydrocarbon product (pyrolysis oil) whose caloric value is many times greater than
the amount of electrical energy used in the operation of the process, as indicated by energy ratios ranging between 2 and 8 (Table 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 ow rate of 5 kg/h,
producing liquid pyrolysis products with an energy content
equivalent to approximately 60 kW. The caloric 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 ratios 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 considered 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 rening of the pyrolysis 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 components). Overall, the results show that the microwave-heated pyrolysis 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 inuenced the concentrations and molecular nature of the different 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 gasoline-like oil product that contains potentially valuable light aliphatic 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 reecting 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 renery as a chemical feedstock for further
processing, although further studies are needed to conrm 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

Author's personal copy

S.S. Lam et al. / Fuel 92 (2012) 327339

oil. This unique combination of properties enables the potential

generation of products with signicant commercial value out of
what would otherwise be a toxic and difcult to dispose of chemical liability.
Acknowledgements
Su Shiung Lam acknowledges the nancial assistance by PublicService-Department of Malaysia Government and University
Malaysia Terengganu.
References
[1] Brinkman DW, Dickson JR. Contaminants in used lubricating oils and their fate
during distillation/hydrotreatment re-rening. Environ Sci Technol
1995;29:816.
[2] Audibert F. Waste engine oils: rerening and energy recovery. 1st
ed. Amsterdam: Elsevier B.V; 2006.
[3] Ramasamy KK, T-Raissi A. Hydrogen production from used lubricating oils.
Catal Today 2007;129:36571.
[4] Song G-J, Seo Y-C, Pudasainee D, Kim I-T. Characteristics of gas and residues
produced from electric arc pyrolysis of waste lubricating oil. Waste Manage
2010;30:12307.
[5] Lam SS, Russell AD, Chase HA. Pyrolysis using microwave heating: a
sustainable process for recycling used car engine oil. Ind Eng Chem Res
2010;49:1084551.
[6] Sinag A, Glbay S, Uskan B, Uar S, zgrler SB. Production and
characterization of pyrolytic oils by pyrolysis of waste machinery oil. J
Hazard Mater 2010;173:4206.
[7] Lam SS, Russell AD, Chase HA. Microwave pyrolysis, a novel process for
recycling waste automotive engine oil. Energy 2010;35:298591.
[8] Nern C, Domeo C, Moliner R, Lzaro MJ, Suelves I, Valderrama J. Behaviour of
different industrial waste oils in a pyrolysis process: metals distribution and
valuable products. J Anal Appl Pyrol 2000;55:17183.
[9] Gmez-Rico MaF, Martn-Gulln I, Fullana A, Conesa JA, Font R. Pyrolysis and
combustion kinetics and emissions of waste lube oils. J Anal Appl Pyrol
2003;6869:52746.
[10] Fernndez Y, Arenillas A, Bermdez JM, Menndez JA. Comparative study of
conventional and microwave-assisted pyrolysis, steam and dry reforming of
glycerol for syngas production, using a carbonaceous catalyst. J Anal Appl Pyrol
2010;88:1559.
[11] Fernndez Y, Arenillas A, Dez MA, Pis JJ, Menndez JA. Pyrolysis of glycerol
over activated carbons for syngas production. J Anal Appl Pyrol
2009;84:14550.
[12] Salema AA, Ani FN. Microwave induced pyrolysis of oil palm biomass.
Bioresource Technol 2011;102:338895.
[13] Arpa O, Yumrutas R. Experimental investigation of gasoline-like fuel obtained
from waste lubrication oil on engine performance and exhaust emission. Fuel
Process Technol 2010;91:197204.
[14] Fuentes MJ, Font R, Gmez-Rico MF, Martn-Gulln I. Pyrolysis and combustion
of waste lubricant oil from diesel cars: decomposition and pollutants. J Anal
Appl Pyrol 2007;79:21526.
[15] Uar S, Karagz S, Yanik J, Saglam M, Yuksel M. Copyrolysis of scrap tires with
waste lubricant oil. Fuel Process Technol 2005;87:538.
[16] Menndez JA, Menndez EM, Garcia A, Parra JB, Pis JJ. Thermal treatment of
active carbons: a comparison between microwave and electrical heating. J
Microwave Power EE 1999;34:13743.
[17] ASTM Standard D2887-08. Standard test method for boiling range distribution
of petroleum fractions by gas chromatography. West Conshohocken, PA: ASTM
International; 2008.
[18] ASTM Standard D1298-99(2005). Standard test method for density, relative
density (specic gravity), or API gravity of crude petroleum and liquid
petroleum products by hydrometer method. West Conshohocken, PA: ASTM
International; 2005.
[19] ASTM Standard D1310-01. Standard test method for ash point and re point
of liquids by tag open-cup apparatus. West Conshohocken, PA: ASTM
International; 2007.
[20] ASTM Standard D445-10. Standard test method for kinematic viscosity of
transparent and opaque liquids (and calculation of dynamic viscosity). West
Conshohocken, PA: ASTM International; 2010.
[21] ASTM Standard D3710-95(2009). Standard test method for boiling range
distribution of gasoline and gasoline fractions by gas chromatography. West
Conshohocken, PA: ASTM International; 2009.

339

[22] ASTM Standard D4809-09a. Standard test method for heat of combustion of
liquid hydrocarbon fuels by bomb calorimeter (precision method). West
Conshohocken, PA: ASTM International; 2009.
[23] Kim SS, Kim SH. Pyrolysis kinetics of waste automobile lubricating oil. Fuel
2000;79:19439.
[24] Menndez JA, Domnguez A, Inguanzo M, Pis JJ. Microwave pyrolysis of sewage
sludge: analysis of the gas fraction. J Anal Appl Pyrol 2004;71:65767.
[25] Domnguez A, Menndez JA, Inguanzo M, Pis JJ. Investigations into the
characteristics of oils produced from microwave pyrolysis of sewage sludge.
Fuel Process Technol 2005;86:100720.
[26] Domnguez A, Menndez JA, Inguanzo M, Ps JJ. Production of bio-fuels by high
temperature pyrolysis of sewage sludge using conventional and microwave
heating. Bioresource Technol 2006;97:118593.
[27] Depeyre D, Flicoteaux C, Chardaire C. Pure n-hexadecane thermal steam
cracking. Ind Eng Chem Proc DD 1985;24:12518.
[28] Seeger M, Gritter RJ. Thermal decomposition and volatilization of poly(aolens). J Polym Sci: Polym Chem Ed 1977;15:1393402.
[29] Westerhout RWJ, Waanders J, Kuipers JAM, van Swaaij WPM. Recycling of
polyethene and polypropene in a novel bench-scale rotating cone reactor by
high-temperature pyrolysis. Ind Eng Chem Res 1998;37:2293300.
[30] Onwudili JA, Insura N, Williams PT. Composition of products from the
pyrolysis of polyethylene and polystyrene in a closed batch reactor: effects
of temperature and residence time. J Anal Appl Pyrol 2009;86:293303.
[31] Ludlow-Palafox C, Chase HA. Microwave-induced pyrolysis of plastic wastes.
Ind Eng Chem Res 2001;40:474956.
[32] Fairburn JA, Behie LA, Svrcek WY. Ultrapyrolysis of n-hexadecane in a novel
micro-reactor. Fuel 1990;69:153745.
[33] Cyprs R. Aromatic hydrocarbons formation during coal pyrolysis. Fuel Process
Technol 1987;15:115.
[34] Williams PT, Besler S. Polycyclic aromatic hydrocarbons in waste derived
pyrolytic oils. J Anal Appl Pyrol 1994;30:1733.
[35] Lzaro MJ, Moliner R, Suelves I, Nern C, Domeo C. Valuable products from
mineral waste oils containing heavy metals. Environ Sci Technol
2000;34:320510.
[36] European Fuels Directive 98/70/EC. Directive 98/70/ec of the european
parliament and of the council of 13 october 1998 relating to the quality of
petrol and diesel fuels and amending directive 93/12/eec. Brussels, Belgium:
European Parliament and Council; 1998.
[37] BS EN 228:2008. Automotive fuels. Unleaded petrol. Requirements and test
methods. London, United Kingdom: British Standards Institution (BSI); 2008.
[38] BS EN 590:2009+A1:2010. Automotive fuels. Diesel. Requirements and test
methods. London, United Kingdom: British Standards Institution (BSI); 2009.
[39] Demirbas A. Gasoline-like fuel from waste engine oil via catalytic pyrolysis.
Energy Sources, A: Recov, Util, Environ Eff 2008;30:143341.
[40] ASTM Standard D975-11. Standard specication for diesel fuel oil. West
Conshohocken, PA: ASTM International; 2011.
[41] Yumrutas R, Alma MH, zcan H, Kaska . Investigation of puried sulfate
turpentine on engine performance and exhaust emission. Fuel 2008;87:2529.
[42] Kim YS, Jeong SU, Yoon WL, Yoon HK, Kim SH. Tar-formation kinetics and
adsorption characteristics of pyrolyzed waste lubricating oil. J Anal Appl Pyrol
2003;70:1933.
[43] Domnguez A, Fernndez Y, Fidalgo B, Pis JJ, Menndez JA. Bio-syngas
production with low concentrations of co2 and ch4 from microwave-induced
pyrolysis of wet and dried sewage sludge. Chemosphere 2008;70:397403.
[44] Moliner R, Lzaro M, Suelves I. Valorization of lube oil waste by pyrolysis.
Energy Fuel 1997;11:116570.
[45] Arpa O, Yumrutas R, Argunhan Z. Experimental investigation of the effects of
diesel-like fuel obtained from waste lubrication oil on engine performance and
exhaust emission. Fuel Process Technol 2010;91:12419.
[46] Arpa O, Yumrutas R, Demirbas A. Production of diesel-like fuel from waste
engine oil by pyrolitic distillation. Appl Energy 2010;87:1227.
[47] Lzaro MJ, Moliner R, Suelves I. Co-pyrolysis of coals and lube oil wastes in a
bench-scale unit. Energy Fuel 1999;13:90713.
[48] Lzaro MJ, Moliner R, Suelves I, Domeo C, Nern C. Co-pyrolysis of a mineral
waste oil/coal slurry in a continuous-mode uidized bed reactor. J Anal Appl
Pyrol 2002;65:23952.
[49] Al-Ghouti MA, Al-Degs YS, Amer M. Determination of motor gasoline
adulteration using FTIR spectroscopy and multivariate calibration. Talanta
2008;76:110512.
[50] Lee KH. Thermal degradation of heavy pyrolytic oil in a batch and continuous
reaction system. J Anal Appl Pyrol 2009;86:34853.
[51] Roqul Islam M, Haniu H, Raqul Alam Beg M. Liquid fuels and chemicals from
pyrolysis of motorcycle tire waste: product yields, compositions and related
properties. Fuel 2008;87:311222.
[52] Romanow S. Fuel trends report: gasoline 19952005. U.S. Environmental
Protection Agency; 2008.