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Journal of Analytical and Applied Pyrolysis xxx (2016) xxx–xxx

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Journal of Analytical and Applied Pyrolysis

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Valorization of spent lubricant engine oil via catalytic pyrolysis:

Influence of barium-strontium ferrite on product distribution and
composition
Imtiaz Ahmad a,∗ , Razia Khan a , Mohammad Ishaq a , Hizbullah Khan b , M. Ismail a,b ,
Kashif Gul a , Waqas Ahmad a
a
Institute of Chemical Sciences, University of Peshawar, 25120 Peshawar, Khyber Pakhtunkhwa, Pakistan
b
Department of Environmental Sciences, University of Peshawar, 25120 Peshawar, Khyber Pakhtunkhwa, Pakistan

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

Article history: The conversion of spent lubricant oil (SLO) into diesel like products over barium-strontium ferrite (BSFO)
Received 12 July 2016 was investigated. The influence of BSFO on the yield and other characteristics of the distillate fractions like
Received in revised form 4 October 2016 individual compounds, hydrocarbon group types, carbon range distribution and potential fuel properties
Accepted 12 October 2016
was the main focus of the study. The results indicated that the catalyzed run with 5% BSFO generated
Available online xxx
light liquid fraction (condensable) in significant yield (86.05 wt%). The composition of the pyrolysis oil
was studied via Fourier Transform Infra-Red spectroscopy (FTIR) and Gas Chromatography–Mass Spec-
Keywords:
trometry (GC–MS). The results indicated the presence of aliphatics (78.34 wt%), olefinics (11.69 wt%),
Used engine oil management
Pyrolysis
naphthenics (5.21 wt%), aromatics (3.51 wt%), oxygenates (0.68 wt%) and halogenated hydrocarbons
Doped ferrites (0.56 wt%) in the catalytically derived liquid fraction which confirmed its suitability as fuel and feed stock
Diesel fuels for petrochemicals. The determined fuel properties of the derived liquid oil also showed conformance
ASTM methods with the petro-diesel which warrants its potential application as premium fuel.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Spent lubricant oil (SLO) is a by-product of formulated oil used
in vehicles and machinery. It is generated in large quantities each
year, hence considered as a high-volume waste. Its careless dis-
posal to the environment has been reported to be detrimental
owing to the presence of undesirable and environmentally objec-
tionable impurities like soot, polycyclic aromatic hydrocarbons and
impurities from additives such as chlorinated paraffins and poly-
chlorinated biphenyls [1,2]. Conventionally, SLO is disposed off
into landfill sites or used for generation of heat via incineration
or thermal decomposition or may be recycled by reclamation and
re-refining for re-use. However, these methods are considered as
impractical due to serious environmental effects, loss of valuable
resource and poor quality of the refined oils [3–5]. Most of the pub-
lished literature is focused on development of substitute methods
[6–9] including pyrolysis. In pyrolysis, the SLO is heated in oxygen
depleted environment and thermally cracked into shorter hydro-
carbons to yield products that can be used as fuel or as chemical feed
∗ Corresponding author.
E-mail address: patwar2001@yahoo.co.in (I. Ahmad).
stocks. Among these, the catalytic pyrolysis has been elaborated in
the open literature and a number of catalysts including sulfated
zirconia [10], zeolites [11–13], alumina [14], perlite & wood ash
[15], and metallic pyrolysis char [16] have been investigated with
greater success. However, the composition of the resulting liquid
products shows non-conformance with the petro-fuels owing to
several reasons including different reaction conditions and choice
of catalyst. Moreover, the quality of the derived oils is not satis-
fied/compatible with the petro-fuels for direct use in an engine and
thus has a poor market value. Furthermore, most of the catalysts
studied were highly expensive and needed regeneration. There-
fore, it is essential to investigate on new, low cost, and durable
catalysts with good catalytic performance for recovery of lighter
hydrocarbons from SLO.
Iron based catalysts are being used in thermolysis and up-
gradation of heavy petroleum residues with greater success
[17–21]. Among this group of catalysts, spinel ferrites, especially
hematite and magnetite are enjoying popularity in a variety of
industrial applications including as catalysts. Alkali and alkaline
earth metals have been reported to be promoters for a variety of
catalysts and also found to be effective in reactions leading to tar
elimination [22–24]. Doping with these alkali/alkaline earth met-

http://dx.doi.org/10.1016/j.jaap.2016.10.008
0165-2370/© 2016 Elsevier B.V. All rights reserved.

Please cite this article in press as: I. Ahmad, et al., Valorization of spent lubricant engine oil via catalytic pyrolysis: Influence of barium-
strontium ferrite on product distribution and composition, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.10.008
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Fig. 1. Schematic of pyrolysis assembly.
als, deep oxidation capabilities of iron catalysts can be minimized
and their cracking abilities can be exposed.
In current study, two metal ions such as barium (Ba2+ ) and stron-
tium (Sr2+ ) were simultaneously doped into the magnetite matrix
and their potential catalytic effects in conversion of SLO into diesel-
like fuels was explored. The catalyst reported in this paper is cost
effective and needs non-precious commercially viable precursors
such iron oxide, barium carbonate and strontium carbonate for its
synthesis.
2. Materials and methods
2.1. Chemicals and reagents
Analytical grade chemicals and reagents i.e. 2-propanol (Merck),
Fe2 O3 , 99% (Sigma Aldrich), BaCO3 , 99% (Alfa Aesar) and SrCO3 , 99%
(Alfa Aesar) were used without further purification. Spent lubricant
oil (PSO DEO 8000 used in bus for 3000 km mileage) was collected
from a local mechanical workshop and subjected to adsorptive
cracking for removal of soot, water, etc. by heating in the presence
of pre-baked clay (PBC) as adsorbent. The clarified SLO was then
used in subsequent pyrolysis experiments.
Fig. 2. Flow sheet of pyrolysis process.
Please cite this article in press as: I. Ahmad, et al., Valorization of spent lubricant engine oil via catalytic pyrolysis: Influence of barium-
strontium ferrite on product distribution and composition, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.10.008
2.2. Preparation of barium-strontium ferrite
BSFO (BaO 0.5 SrO 0.5 Fe12 O19 ) was synthesized in laboratory
by slurry milling method. In a typical procedure, stoichiometric
amounts of barium carbonate (BaCO3 ) and strontium carbonate
(SrCO3 ) were mixed with iron (III) oxide (Fe2 O3 ) in a small amount
of solvent (2-propanol + water) in order to get slurry. The resul-
tant slurry was thoroughly mixed using stainless steel balls (5 mm)
for a period of 4 h in order to get homogeneity. The homogeneous
phase was subsequently dried in an oven at 80–120 ◦ C for 18 h to
get a cake. The resultant cake was then ground to a fine powder
and sieved through 70 mesh. The powder phase was mechanically
pressed into a thin disc and calcined in air at 900 ◦ C at a heating
rate of 5 ◦ C min−1 for 3 h in a muffle furnace. The final product was
ball milled into pulverized powder and stored for characterization
and activity tests.
2.3. Pyrolysis of spent lube oil
The schematic of pyrolysis set up is provided in Fig. 1 and process
flow diagram is outlined in Fig. 2. The assembly consisted of:
1. micro steel reactor (A)
2. tube furnace (B)
3. nitrogen cylinder (C)
4. Liebig condenser (D) provided with water inlet (E) and outlet (F).
5. receiving flask (G)
6. Gas outlet (H).
In a typical run, a slurry of SLO and PBC prepared in ratio of
1:2 (w/w) was taken into a steel reactor (2.1 cm diameter × 25.4 cm
height) fitted into a tube furnace. The reactor was flushed 2–3 times
with a purge of nitrogen in order to eliminate air and then heated.
The cracked vapors were condensed by passing through a Liebig
condenser (D). The condensates were collected in a receiving flask
as liquid oil and weighed. The non-condensable gas fraction was
sent to exit. The assembly was then cooled to ambient tempera-
ture and opened. The residue inside reactor was carefully collected
and weighed. The yields (overall, liquid, gas and coke/residue) were
defined as Eqs. (1)–(4).
MO − MR
Overall conversion (wt%) = × 100 (1)
MO
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Fig. 3. EDX signature of barium-strontium ferrite.
ML
Liquid (wt%) = × 100
MO
Gas (wt%) = 100 − [%ML + %MR]
MR
Residue (wt%) × 100
MO
Where;
MO: mass of the feed oil
ML: mass of the liquid oil
MR: mass of the residue/char.
Thermal pyrolysis was carried out under experimental con-
ditions of SLO/PBC ratio; 1:2, temperature; 500 ◦ C, heat rate;
10 ◦ C min−1 , residence time; 90 min, and nitrogen flow rate of
1 L min−1 . The thermally derived liquid oil was subjected to
catalytic pyrolysis over BSFO carried out under same set of experi-
mental conditions where catalyst concentration was varied from 1
to 5%.
2.4. Analyses and characterization
2.4.1. Characterization of barium-strontium ferrite
The morphological & the elemental characterizations of the
BSFO were performed by using scanning electron microscope
equipped with energy dispersive x-ray (model JEOL-Jsm-5910;
Japan). The instrument was provided with Schottky field emis-
sion source which produces an electron probe with a diameter of
about 3 to 8 nm directed at sample. The accelerating voltage and
emission current used in SEM imaging were 15 kV and 6 nA, respec-
tively. The samples were mounted on stubs, kept at a working
distance of 19.8–22.4 mm, and tilted at an angle of 30◦ from primary
electron beam to face electron energy analyzer. Crystallographic
and phase analyses were carried out by using x-ray diffractome-
ter (XRD; model JDX-9C, JOEL, Japan). The powder was scanned
through 2 angle range of 10–80◦ using a CuK␣ radiation detec-
tor. Surface and pore size distribution were investigated by surface
area analyzer (Quantachrome Nova Station A). Before analysis, sam-
ple was degassed for about 4 h upto 200 ◦ C. The surface area was
measured from nitrogen adsorption-desorption isotherms using
Brunauer–Emmett–Teller (BET equation) [25,26]. The pore size
and pore volume were calculated through Barrett–Joyner–Halenda
(BJH) model [27].The FT-IR analysis was carried out by using dou-
ble beam FTIR spectrophotometer model Shimadzu FTIR-820.1
PC, using KBr pellets of the sample. Absorbance was recorded as
average of three readings in the range of 4000–400 cm−1 . The
Please cite this article in press as: I. Ahmad, et al., Valorization of spent lubricant engine oil via catalytic pyrolysis: Influence of barium-
strontium ferrite on product distribution and composition, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.10.008
3
thermal stability (durability) of the catalyst was evaluated by ther-
(2)
mogravimetric analyzer (TGA) using TGA analyzer (TGA/SDT 85e
Mettler Toledo-Switzerland). The sample was heated at a rate of
(3)
10/◦ C min−1 under O2 atmosphere at (50 mL min−1 ) from ambient
to 500 ◦ C.
(4)
2.4.2. Analysis of distillate fractions
Compositional study by FTIR and GC–MS: The compositions of
distillate fractions were investigated by Fourier Transform Infra
Red spectroscopy (FTIR Prestige-21 Shimadzu, Japan). Individual
hydrocarbons, hydrocarbon group types and carbon number dis-
tributions of resultant distillate fractions were investigated by Gas
Chromatographic–Mass Spectrometry (GC–MSQP 2010 Shimadzu),
equipped with DB-5MS column (25 m × 0.25 mm i.d., 0.25 ␮m). The
temperature programming used was:
i. ramp of initial oven temperatures to 100 ◦ C at a rate of
5 ◦ C min−1 with 5 min hold.
ii. second ramp to 150 ◦ C at a rate of 10 ◦ C min−1 and 10 min hold
time.
iii. final ramp in temperature was upto 290 ◦ C at the rate of
2.5 ◦ C min−1 with an isothermal 10 min hold.
The individual compounds were identified from the GC–MS
peaks by using the data of National Institute of Standards and
Technology-Mass Spectral (NIST-MS) Library. The compounds were
quantified as% total ion content (TIC); an integration of the chro-
matogram’s peaks.
Fuel properties: The commonly used fuel properties (density,
specific gravity, API gravity, Conradson carbon residue, ash, kine-
matic viscosity, pour point, diesel index, cetane number and heat
of combustion) of the distillate fractions were investigated using
American Society for Testing and Materials (ASTM)/Institute of
Petroleum (IP) designated methods [28,29]. Each experiment was
performed in triplicate and the mean values are reported.
3. Results and discussion
3.1. Characterization of barium-strontium ferrite
The elemental study was performed by EDX. The signatures are
provided in Fig. 3 and the corresponding data is given in Table 1.
The results indicated that elements like C, O, Fe, Sr and Ba occurred
in concentrations of 5.24, 24.40, 59.70, 0.85 and 9.80%, respec-
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Table 1
Elemental composition of barium-strontium ferrite.

element weight%

C 5.24
O 24.40
Fe 59.70
Sr 0.85
Ba 9.80
total 100.00

Fig. 6. BET plot of barium-strontium ferrite.

Table 2
Surface properties of barium-strontium ferrite.

property level

BET surface area (m2 g−1 ) 3.3879

BJH surface area (m2 g−1 ) 3.7778
pore diameter (Å) 62.804
pore volume (cm3 g−1 ) 0.004138

Fig. 4. SEM micrograph of barium-strontium ferrite (Magnification 8000×).

matched with the standard JCPDS-51-1879 pattern of crystalline

tively. Further, the elemental composition was found to be similar
to its theoretical concentration. The morphology was studied by
SEM. The micrograph provided in Fig. 4 showed some fine grains
of variables sizes (average size of ∼2 ␮m), as well as some defects
and cracks distributed through the micrograph can also be seen.
The small granules can be seen as agglomerates and stacked over
the surface of the large grains. The phase analysis was carried
out by XRD. The diffractogram is shown in Fig. 5, which fea-
tured several diffraction peaks at 2 planes of Ba-Sr crystallites.
The major peaks were appeared at 2␪ (32.45), (33.85), (34.25),
(35.5), (37.05), (40.55), (55.25), (56.5), and (63.1). The diffractogram
Ba0.5 Sr0.5 Fe12 O19 . Some sharp peaks corresponded to magnetite
can also be observed. The surface area measurement from nitrogen
adsorption-desorption curves (Fig. 6) given in Table 2 demon-
strated a sintered structure with fair micro porous properties.
The FT-IR spectrum (Fig. 7) showed major absorption peaks at
1400, 2350, 3130 and 3620 cm−1 . A bunch of minor peaks appeared
in wave number range of 500 to 650 cm−1 are characteristic of Fe O
absorption due to the symmetric stretching vibration of Fe O. The
peak centered at 1400 cm−1 corresponded to carbonate group or
adsorbed CO. Peaks at 2320 and 3130 cm−1 showed adsorbed CO2
and O H stretching vibrations. A broad peak at 3600 cm−1 indi-

Fig. 5. Diffractogram of barium-strontium ferrite.

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Fig. 7. FT-IR spectrum of barium-strontium ferrite.
Fig. 8. TGA profile of barium-strontium ferrite.
cated stretching of adsorbed H2 O molecules. The acidity of the
catalyst can be ascribed to Fe OH surface functions.
The TGA profile (Fig. 8) indicated that there is a very minor
weight loss of ∼0.18 mg (2%) in temperature range of 350 to 490 ◦ C
which may be attributed to the calcination of unreacted carbonate
precursors. No further weight loss can be observed in the profile,
which indicated its thermal stability at the reaction temperature
selected for pyrolysis of SLO.
3.2. Catalysts activity tests
The pyrolysis of the SLO was carried out under the optimized
conditions as reported by our group elsewhere [30] i.e. temper-
ature; 500 ◦ C, PBC/SLO ratio; 1:2, residence time; 90 min and a
reasonable amount of the distillate fraction was obtained, which
was then subjected to catalytic pyrolysis (over BSFO used in differ-
ent concentrations ranged from 1 to 5 wt%). The optimum catalyst
concentration was decided from the maximum yield of the distillate
fraction. Using the optimum experimental conditions, the distillate
fractions (from both thermal and catalyzed runs) were collected in
Please cite this article in press as: I. Ahmad, et al., Valorization of spent lubricant engine oil via catalytic pyrolysis: Influence of barium-
strontium ferrite on product distribution and composition, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.10.008
5
Table 3
Overall conversion and yields of liquid, gas and solid residue derived from pyrolysis
of spent lubricant oil as a function of barium-strontium ferrite concentration.
run catalyst yields (wt%)
amount
(wt%)
overall liquid gas solid
residue/coke
thermal – 99.20 95.60 3.60 0.80
BSFO-catalyzed 1 99.01 32.45 66.56 0.99
2 98.04 72.012 26.02 1.96
3 97.09 60.82 36.27 2.91
4 96.15 77.66 18.49 3.84
5 95.23 86.05 9.17 4.76
SLO/PBC ratio; 1:2, temperature; 500 ◦ C, heat rate; 10 ◦ C min−1 , residence time;
90 min, and nitrogen flow rate of 1 Lmin−1.
bulk amount, submitted to compositional analysis and fuel prop-
erties determination in comparison with the petro-diesel so as to
check their suitability as diesel-like fuel.
The yield data including overall conversion and yields of liq-
uid, gas and residue, as a function of barium-strontium ferrite
concentration in comparison with the un-catalyzed thermal run
is provided in Table 3. The results showed an overall conversion
of 99.2%, in the thermal run whereas the yields of liquid, gas and
solid residue were found to be 95.6, 3.6 and 0.8%, respectively. It
can be observed that by using barium-strontium ferrite, the over-
all yield decreased with the increase in its amount. The maximum
overall conversion of 99.01% was obtained with 1 wt% BSFO, which
decreased gradually with the increase in amount of the catalyst and
attained a level of 95.23% at 5 wt% BSFO.
The liquid yields were found to be decreased in all of the
catalyzed runs in comparison with the thermal run. Among the
catalyzed runs, maximum yield of 86.05% was obtained with 5 wt%
catalyst. As far as the gas formation is concerned, the catalyst caused
the gas yields to increase which attained a maximum level of 66.56%
with 1 wt% catalyst. The yield pattern showed a decrease with the
increase in catalyst amount beyond 1% and declined by attaining
the level of 9.17% with 5% BSFO. The solid residue followed the
yield pattern on contrary to that of the gas and showed an increase
with the increase in the amount of the catalyst. A maximum yield
of 4.76% was observed with 5 wt% catalyst. It can be deduced from
the results that the high gas and residue yields are at the expense
of the liquid fraction compared with the thermal run.
Several reasons can be thought for this product distribution.
The catalyst may have facilitated the secondary decomposi-
tion/cracking reactions and have formed products mostly in the
gas phase. High gas yields are caused by the secondary decompo-
sition reactions as reported earlier [31]. Furthermore, the catalyst
might have favored poly condensation reactions and have caused
the residue/char yields to increase. Poly condensation reactions
usually lead to a more stable char [32]. It has already been reported
elsewhere that under the cracking conditions, some reactions cause
the formation of aromatics, when they reach to a critical concentra-
tion in the reaction mixture; they get separate from the liquid phase
and form coke rapidly [33]. The variation in product distribution in
thermal and catalyzed runs can also be attributed to the different
mechanisms involving bond scissions. The bond scission occurs at
certain definite locations in catalytic reactions but randomly occurs
in thermal reactions [34]. The ␤-scission reaction is the primary
reaction in fluid catalytic cracking, which occurs by breakage of
␤ C C bond, and various secondary reactions such as alkylation,
hydrogenation, isomerization and condensation [35]. Such kind of
bond scissions followed by secondary reactions can be thought a
valid reason for change in product distribution between the two
runs. The generalized reaction mechanism is depicted as follows:
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Fig. 9. FT-IR spectra of the distillate fractions derived from pyrolysis of spent lubri-
cant oil (a) thermal run (b) barium-strontium ferrite catalyzed run.

It can also be observed that the yield of the distillate frac-

tion is quite significant compared to the previous studies carried
out on petroleum residues using different iron based catalysts
[17–21], which indicated the effectiveness of barium-strontium
ferrite. The high activity may be due to the presence of the bar-
ium and strontium which may have influenced its acidity and pore
size distribution. Barium and strontium have been reported to keep
the pores open for bulky molecules of the catalysts and enhance its
performance by the deactivation of external acid sites with keep-
ing the internal acid sites active, and by controlling the size of
pore-entrances and channels of the catalyst [36].
It is inferred from the results that the BSFO functioned effec-
tively in formation of the gas when used in low concentration and
gave more distillate fraction, residue and less gas when used in high
concentration due to frequent cracking and recombination reac-
tions. Based on the reasonable liquid yield, the barium-strontium
ferrite was found to be more active when used in high concentration
(5 wt%).
3.3. Compositional study and fuel properties
The detailed compositional information of the crude oil and
oil products in terms of paraffinic, olefinic, naphthenic, aromatic
hydrocarbons and hetero-compounds is becoming increasingly
important [37–40] before recommending a sample as fuel. There-
fore, the distillate fractions derived from the thermal and catalyzed
runs were submitted to compositional study by FT-IR and GC–MS.
FTIR is a recognized tool used for characterization of pyroly-
sis products [41–45]. The FT-IR spectra of the fractions understudy
is/are given in Fig. 9(a) & (b). The corresponding peak data and
assigned configurations are displayed in Table 4. The spectro-
gram of the thermal run exhibited strong intensity peaks in the
wave number range of 2922, 2852 and 1463 cm−1 which showed
methyl hydrogen in aromatic configurations. In addition, the two
medium intensity peaks centered at 2953, and 1680 cm−1 showed
naphthenic configurations with chain methylene C H stretching
vibrations, as well as the methyl C H stretching vibration. Some
week peaks centered at 1540, 1540, and 721 cm−1 are observable
which showed aldehydes, ketones, acids, aromatic and hetero-
cyclic compounds. The spectrogram of the catalyzed run is given
in Fig. 9(b) which exhibited same peaks as observed in that of
thermal run. The peak positions remained un-changed, however,
the intensity of some peaks decreased. The results showed that
both fractions consisted of aliphatic, olefinic, aromatic hydrocar-
bons along with oxygenates like aldehydes, ketones, ethers and
alcohols.
The mass spectroscopy has been reported as a recognized tool
for the identification of saturates, olefins, naphthenes, and aro-
matics in a fuel sample [46]. In order to have an insight into the
composition of the derived fractions and to determine their suit-

Table 4
Absorption peaks in FT-IR spectra of the distillate fraction derived from thermal and barium-strontium ferrite (5%) catalyzed pyrolysis of spent lubricant oil.

run position (cm−1 ) intensity assigned configuration

thermal 2953 medium C H (CH3 ) aliphatic

2922 strong C H (CH3 ) aliphatic
2852 strong C H (CH2 ) aliphatic
1680 medium C C (stretch) olefinic
1640 weak C C (stretch) olefinic
1540 weak C C (stretch) aromatic
1463 strong CH3 (bend) aliphatic
721 weak CH2 (bend) aliphatic

catalyzed 2954 medium C H (CH3 ) aliphatic

2922 strong C H (CH3 ) aliphatic
2853 strong C H (CH2 ) aliphatic
1658 weak C C (stretch) olefinic
1620 weak C C (stretch) aromatic
1540 weak C C (stretch) aromatic
1456 strong CH3 (bend) aliphatic
1375 strong C H (bend) aliphatic
721 medium CH2 (bend) aliphatic

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Fig. 10. GC–MS profiles of the distillate fractions derived from pyrolysis of spent lubricant oil: (a) thermal run (b) barium-strontium ferrite catalyzed run.

ability as candidate fuel in commercial applications, the GC–MS

analysis was performed. The existence of most of the compounds
occurred in commercial petro-diesel including individual hydro-
carbons, hydrocarbon group types and carbon range distributions
was checked by using semi quantitative method [47]. Different
kinds of the individual hydrocarbons like paraffins, olefins, naph-
thenes, aromatics, oxygenated and alkylated hydrocarbons were
identified. The GC–MS profiles of the thermal and catalyzed runs
are compiled in Fig. 10(a) & (b) and the corresponding data is
given in Table 5. The two fractions possessed all most analo-
gous compositions. Among the paraffins, the individual compounds
determined in high concentration (1% to as high as 6.8%) included
heptane, 3-ethyl-2,4-dimethyl pentane, octane, nonane, decane,
undecane, dodecane, tridecane, tetradecane, pentadecane, hexade-
cane, heptadecane, octadecane, nonadecane, eicosane, henicosane,
docosane, tetracosane and pentacosane. Alkyl derivatives of these
compounds were also found and each was present in small pro-
portion (<1%). Most of these compounds are reported to have
impact on several properties of diesel fuels [48]. The major olefins
each occurred in concentration of >2 wt% included l-heptene, 2-
pentene, 2,3,4-trimethyl, 1-heptene, 2-methyl, l-octene, 1-nonene
and 1-decene. Some higher molecular weight olefins such as 3-
hexadecene and their alkyl derivatives were also detected each
occurred in concentration of <0.5 wt%. The naphthenic hydrocar-
bons determined included major compounds like cyclohexene,
cyclobutane, 1-methyl cyclohexane, 1-methyl-3-propyl cyclohex-
ane, l-ethyl-2-heptyl cyclopropane, and nonylcyclopropane, each
occurred in concentration of <1 wt%. Higher naphthenes included
cyclotetradecane and cyclotetracosane were determined in low
concentrations. The major aromatic compounds identified included
toluene, naphthalene, phenanthrene and their alkyl derivatives.
Some prominent derivatives detected were ethylbenzene, benzene,
1,3-dimethyl, benzene, l-ethyl-3-methyl, benzene, 1-methyl-3-(l- Fig. 11. Compositional study of distillate fractions derived from thermal and
barium-strontium ferrite (5%) catalyzed pyrolysis of spent lubricant oil: (a) hydro-
methylethyl),1,8-dimethyl naphthalene and 2,6-dimethyl naph- carbon group types (b) carbon range distributions.
thalene. Each individual aromatic compound occurred in <0.8 wt%
concentration in the two fractions. Oxygenated hydrocarbons,
mostly alcohols detected were 3-nonene-1-ol, indene 2,3-dihydro- The distributions (as wt%) of the paraffins (P), olefins (O),
l,2-dimethyl and 1-decanol, 2-hexyl and each compound was found naphthenes (N) & aromatics (A) (collectively denoted as PONA),
in <0.5 wt% concentration. The fractions also contained octadecane, oxygenated and halogenated hydrocarbons were calculated from
1-iodo (alkyl halide) in 0.55 wt% concentration. Most of the com- the corresponding peak area. The results are compiled in Fig. 11(a)
pounds determined in fractions understudy have been reported to which showed that in comparison to the thermal run, the yield
be essential components of petro-diesel [49]. Overall, the compo- pattern of PONA slightly altered, the paraffins decreased to 78%,
sitions are in conformity with the petro-diesel with some minor whereas the olefins increased marginally to 11%, and naphthenes
variations which may be due to many factors including intrinsic increased to 5%. The aromatic contents also increased upto 3.51%.
reactivity, physio-sorption and vapour–liquid equilibrium in the The oxygenates and alkyl halides slightly declined to 0.68 and
reaction environment [50]. 0.56%, respectively. As reported elsewhere, olefins are resulted at

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Table 5
Individual compounds identified by GC–MS in the distillate fractions derived from thermal and barium-strontium ferrite (5%) catalyzed pyrolysis of spent lubricant oil.

Entry Name of Compound Thermal Run Catalyzed run

R. T(Min) area conc. (%) R. T(Min) Area Conc. (%)

Paraffins
1. heptane 3.183 129951 1.53 3.186 442193 1.23
2. octane, 2,5-dimethyl- 4.917 32230 0.38 4.926 218131 0.61
3. heptane, 3-methyl- 5.186 15321 0.18 5.194 86107 0.24
4. octane 6.232 80354 0.95 6.243 534079 1.49
5. octane, 4-methyl- 8.752 15804 0.19 8.764 104670 0.29
6. octane,3-ethyl-2,7-dimethyl- 8.833 15268 0.18 8.845 107369 0.30
7. nonane 10.231 81809 0.97 10.248 549454 1.53
8. pentane,3-ethyl-2,4-dimethyl- 10.902 202144 2.39 10.937 199739 0.56
9. octane, 2,6-dimethyl- – – 11.53 102287 0.28
10. nonane, 2-methyl- 12.561 26508 0.31 12.712 113530 0.32
11. nonane, 3-methyl- 12.923 18098 0.21 12.94 116825 0.33
12. decane 13.993 95123 1.12 14.012 607805 1.69
13. octane, 2,3,6-trimethyl- 14.75 7425 0.09 14.767 49063 0.14
14. heptane, 2,5,5-trimethyl- 16.061 10321 0.12 16.077 72397 0.20
15. nonane, 3,7-dimethyl- 16.409 14372 0.17 16.427 111930 0.31
16. nonane, 2-methyl-3-methylene 17.277 18114 0.21 17.296 101802 0.28
17. undecane 17.394 118525 1.40 17.414 705857 1.96
18. undecane, 5-methyl- 19.544 17735 0.21 19.496 14612 0.04
19. undecane, 3-methyl 19.741 16360 0.19 19.758 114192 0.32
20. dodecane 20.605 110461 1.30 20.624 688558 1.92
21. undecane,2,6-dimethyl- 20.928 30939 0.37 20.942 219233 0.61
22. undecane, 3,9-dimethyl- 22.255 31627 0.37 22.271 188362 0.52
23. tridecane 22.86 126278 1.49 22.876 758919 2.11
24. tridecane, 6-methyl- 23.764 36264 0.43 23.779 230420 0.64
25. tridecane, 4-methyl- 23.905 13548 0.16 23.919 86701 0.24
26. tridecane, 3-methyl- 24.121 27310 0.32 24.136 151043 0.42
27. tetradecane 24.661 171510 2.02 24.681 926799 2.58
28. tetradecane, 3-methyl- 26.116 32047 0.38 26.141 183289 0.51
29. decane, 5-propyl – – – 28.325 173806 0.48
30. pentadecane 26.845 272563 3.22 – – –
31. undecane,2-cyclohexyl- 28.419 12966 0.15 28.453 98854 0.28
32. pentadecane, 4-methyl- 28.493 31822 0.38 28.527 150404 0.42
33. hexadecane 30.021 380863 4.50 30.069 1524063 4.24
34. dodecane, 2,6,11-trimethyl 32.519 31034 0.37 32.582 140518 0.39
35. heptadecane, 2,6,10, 15-tetramethyl 33.224 67595 0.80 33.284 307493 0.86
36. heptadecane 35.05 47823 0.56 34.969 2333968 6.50
37. heptadecane, 8-methyl- 37.193 87240 1.03 37.254 417677 1.16
38. heptadecane,2-methyl- 38.285 65730 0.78 38.334 313872 0.87
39. heptadecane, 3-methyl- 38.662 64312 0.76 38.714 285396 0.79
40. octadecane 40.182 635968 7.51 40.247 2185376 6.08
41. tritetracontane 40.47 96136 1.13 40.531 385075 1.07
42. tetratriacontane 43.241 75144 0.89 43.296 314028 0.87
43. nonadecane 44.961 761731 8.99 45.028 2445818 6.81
44. eicosane 49.328 704026 8.31 49.394 2276966 6.34
45. henicosane 53.352 663039 7.83 53.417 2084839 5.80
46. hentriacontane 55.728 76117 0.90 55.792 269101 0.75
47. pentatriacontane 56.047 178204 2.10 56.111 431456 1.20
48. docosane 57.119 585087 6.91 57.191 1815613 5.05
49. octacosane 59.673 113960 1.34 59.726 357716 1.00
50. tetracosane 64.195 72761 0.86 64.111 989545 2.75
51. pentacosane 67.25 261908 3.09 67.324 627354 1.75
52. hexacosane 70.452 106034 1.25 70.404 435661 1.21
total 81.3 total 78.34

Olefins
53. 1-hexene,2-methyl- 2.978 63183 0.75 2.978 231695 0.64
54. l-heptene 3.032 107074 1.26 3.037 321336 0.89
55. 2-heptene, (e) 3.334 12288 0.15 3.338 86097 0.24
56. l-hexene,2,3-dimethyl- 3.969 40997 0.48 3.976 124838 0.35
57. 1-octene,3,7-dimethyl- 4.646 13474 0.16 4.652 78923 0.22
58. 2-pentene, 2,3,4-trimethyl- 5.409 74245 0.88 5.418 265471 0.74
59. l-heptene, 2-methyl- 5.71 53896 0.64 5.719 281090 0.78
60. 1-octene 5.902 42980 0.51 5.911 263434 0.73
61. 2-hexene,2,5-dimethyl- 6.5 15633 0.18 6.511 92114 0.26
62. 2-octene, (e) 6.788 8019 0.09 6.799 44398 0.12
63. l-heptene,2,4-dimethyl- 7.823 6385 0.08 7.834 16137 0.04
64. l-heptene, 2,6-dimethyl- 8.204 22038 0.26 8.217 119184 0.33
65. l-nonene 9.901 44027 0.52 9.916 239875 0.67
66. 4-nonene 10.462 20617 0.24 10.478 129577 0.36
67. 1,3-hexadiene, 3-ethyl-2-methyl, (z) 10.578 3501 0.04 – – –
68. 1-nonene,2-ethyl- 13.46 30017 0.35 13.477 154192 0.43
69. 1-decene 13.689 42776 0.50 13.709 224273 0.62
70. 3-nonene,2-methyl- 13.887 17480 0.21 13.903 104051 0.29

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Table 5 (Continued)

Entry Name of Compound Thermal Run Catalyzed run

R. T(Min) area conc. (%) R. T(Min) Area Conc. (%)

71. 2-decene, (e) 14.199 9037 0.11 14.218 56853 0.16

72. 2-hexadecene, 2,6,10, 14-tetramethyl- 14.477 19554 0.23 14.494 98282 0.27
73. 2-decene, 8-methyl, (z) 16.136 6585 0.08 16.156 31161 0.09
74. 2-undecene, (e) 17.566 11709 0.14 17.584 71198 0.20
75. 2- dodecene, (e) 17.824 7498 0.09 17.841 45407 0.13
76. 2-decene, 5-methyl, (z) 19.178 24626 0.29 19.199 157742 0.44
77. undecene, 2-methyl- 20.185 28657 0.34 20.203 149464 0.42
78. 1-dodecene 20.743 14892 0.18 20.76 75204 0.21
79. 1-dodecene, 2- methyl- 22.564 22060 0.26 22.578 125497 0.35
80. 3-hexadecene, (z) 22.709 41941 0.50 22.724 241555 0.67
81. 7- tetradecene, (z) 22.954 12459 0.15 – – –
82. 9-octadecene, (e) 24.519 38161 0.45 24.537 216068 0.60
83. 1- tetradecene 26.658 29003 0.34 26.685 157287 0.44
total 10.46 total 11.69

Naphthenes
84. cyclohexene 2.875 27111 0.32 2.878 106937 0.30
85. cyclobutane, (l-methylethylidene) 4.48 18888 0.22 4.487 137377 0.38
86. cyclohexene, l-methyl- 5.076 21896 0.26 6.51 97957 0.27
87. l-cyclohexene , 1,3-dimethyl 7.142 6770 0.08 7.152 54561 0.15
88. cyclohexene, 3,5-dimethyl- 7.212 6244 0.07 7.224 47549 0.13
89. cyclopentane, 1-methyl-2-(2-propenyl), trans 7.543 10287 0.12 7.555 78014 0.22
90. cyclohexane, 1,1 ,3-trimethyl 7.7 2836 0.03 7.713 15591 0.04
91. cyclopentene, l-propyl- 8.016 8362 0.10 8.03 52146 0.15
92. cyclohexene,4-ethyl- 8.924 8845 0.10 11.369 40116 0.11
93. cyclohexane, propyl- 11.353 5845 0.07 – – –
94. cyclopentene,l-(2-methylpropyl) 11.978 10812 0.13 11.996 74239 0.21
95. cyclohexane, l-methyl-3-propyl- 13.364 18528 0.22 13.381 100073 0.28
96. cyclohexane, butyl- 15.084 8005 0.09 15.101 51287 0.14
97. cyclopropane, l-ethyl-2-heptyl- 17.125 51339 0.61 17.144 254120 0.71
98. cyclopropane, nonyl- 20.383 53081 0.63 20.401 266224 0.74
99. cyclododecane 24.746 7851 0.09 24.763 53378 0.15
100. cyclooctacosane 25.687 23195 0.27 25.711 128473 0.36
101. cyclohexane, 2-butyl-l, 1,3-trimethyl- 26.971 5238 0.06 26.998 47272 0.13
102. cyclohexane, 1,2,3-trimethyl- 26.968 5713 0.07 – – –
103. cyclopentane, 3-hexyl-l, l-dimethyl- 29.479 15844 0.19 29.519 102916 0.29
104. cyclotetradecane 34.494 18781 0.22 – – –
105. cyclotetracosane 39.832 28987 0.34 39.883 162983 0.45
total 4.19 total 5.21

Aromatics
106. toluene 5.006 69840 0.82 5.017 294441 0.82
107. ethylbenzene 8.631 30445 0.36 8.647 126861 0.35
108. benzene, 1,3-dimethyl- 9.011 37977 0.45 9.028 210344 0.59
109. benzene, l-ethyl-3-methyl- 13.163 16574 0.20 13.183 82231 0.23
110. benzene, 1,2,4-trimethyl- 14.7 14114 0.17 14.725 79945 0.22
111. benzene, 1-ethyl-2,3-dimethyl- 16.586 7683 0.09 16.61 50976 0.14
112. benzene, l-methyl-3-(1-methylethyl) 16.678 9500 0.11 16.701 64026 0.18
113. benzene, (1, l-dimethyl propyl) 19.871 5542 0.07 19.892 38028 0.11
114. naphthalene, 1,8-dimethyl- 25.224 17052 0.20 25.249 92717 0.26
115. naphthalene, 2,6-dimethyl- 25.317 11157 0.13 25.342 61318 0.17
116. phenanthrene 39.034 38940 0.46 39.084 156737 0.44
total 3.06 total 3.51

Oxygenates
117. 3-nonen-l-ol, (E) 10.574 7403 0.09 10.594 44672 0.12
118. 1-nonanol,4,8-dimethyl- 21.724 10577 0.12 20.293 142172 0.40
119. 1-decanol,2-hexyl- 24.921 5391 0.06 21.738 58830 0.16
total 0.27 total 0.68

Alkyl halide
120. octadecane, 1- iodo 51.619 53891 0.64 51.672 201321 0.56
total 0.56

SLO/PBC ratio; 1:2, temperature; 500 ◦ C, heat rate; 10 ◦ C min−1 , residence time; 90 min, and nitrogen flow rate of 1 L min−1.

the expense of aliphatic hydrocarbons [51]. Further, saturates are
also more vulnerable to secondary decomposition reactions than
other group types hydrocarbons [31]. The catalyst under study
might have assisted such reactions which are responsible for the
formation of olefins.
The influence of BSFO on the yields of hydrocarbons fallen within
the carbon range of C6 –C12 , C13 –C16 , C17 –C20 , C21 –C30 and >C30 was
studied. The results are compiled in and Fig. 11(b) which indicated
that the relative distributions of the different carbon range prod-
ucts in the catalytically derived fraction did not alter to a greater
extent and only the C6 –C12 range hydrocarbons slightly increased
(16%) while that of C13 –C16 range hydrocarbons decreased (15.8%)
compared to the thermal run. As reported elsewhere that metal
oxides can improve the oil quality by promoting the adsorption and
thermal decomposition of the oil [52,53]. The barium-strontium
ferrite might have favored adsorption followed by thermal decom-
positions and have caused formation of the lighter products i.e.
C6 –C12.

Please cite this article in press as: I. Ahmad, et al., Valorization of spent lubricant engine oil via catalytic pyrolysis: Influence of barium-
strontium ferrite on product distribution and composition, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.10.008
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Table 6
Fuel properties of the distillate fractions derived from thermal and barium-strontium ferrite (5%) catalyzed pyrolysis of spent lubricant oil.
Fuel Property Thermal Run
density @ 15 ◦ C (g/cm3 ) 0.91
gravity, specific 0.92
gravity, API @ 60 ◦ F 22
ash (%wt) 0.058
kinematic viscosity @ 40 ◦ C (mm2 /s) 2.00
pour point (◦ C) −5
aniline point (◦ F) 188.6 (87 ◦ C)
diesel index 41
cetane number* 45.30
calorific value (MJ/kg) 39
*
cetane number was calculated as: 0.72 × diesel index +10.
Physico-chemical analysis, are usually recommended for quality
assessment/characteristics of fuels produced at a refinery. Standard
specifications recommended by ASTM were applied to the derived
liquid fractions under study. The results obtained are provided in
Table 6 and compared with the properties of the standard petro-
diesel. Petroleum refinery products are usually classified as light,
middle and heavy fractions. Density is one of the basis for this clas-
sification owing to the fact that density and boiling range go hand
in hand. Furthermore, highly aromatic light fractions may have a
higher density than highly paraffinic middle distillate fractions and
some highly aromatic middle distillate fractions may have a higher
density than some highly paraffinic heavy fractions [54]. The den-
sity of the thermally derived fraction was found to be 0.91 g/cm3
while that of the catalytically derived fraction was 0.89 g/cm3 . It can
be observed that the density of the catalyzed fraction is in close con-
formity with the diesel oil (0.865 g/cm3 ). The results of the specific
gravity are also in conformity with the diesel fuel. The API gravities
occurred within the range of 22 to 27 ◦ API, which showed that the
fractions are enriched in lighter chemical constituents. However,
the values showed non-conformance with the diesel oil, which
typically have 39 to 44 ◦ API. The ash contents determined in both
fractions were negligible and even below detection particularly for
the catalytically derived fraction. The viscosity results are identical
in the two fractions and in agreement with the ASTM specification
and those reported for neat petro-diesel [51]. The pour point was
determined to be −5 ◦ C for thermal run while <−6 for the catalyzed
run. The results indicated excellent cold flow properties. The aniline
point determined for the two distillate fractions were 87 and 84 ◦ C,
respectively which indicated their aliphatic nature. The diesel index
was found to be 41 for thermally derived fraction and 50.6 for cat-
alytically derived fraction. The values are falling within the range of
a diesel fuel. The cetane numbers were also determined and found
to be within the range of a diesel fuel. The calorific value, a param-
eter which describes the heat content present in a fuel determined
in case of the two fractions were found to be in conformity with the
diesel fuel and indicated their excellent combustion properties for
heat generation.
In nutshell, both fractions particularly the catalytically derived
fraction showed best agreement with the standard diesel fuel prop-
erties. The fractions can be recommended for use in commercial
applications as diesel fuel or as blends to the middle distillate frac-
tion obtained as a refinery product.
4. Conclusions
The barium-strontium ferrite did not increase the yield of the
distillate liquid product in comparison with the thermal run, how-
ever, it exhibited an influence on the composition of the resultant
liquid product in terms of the paraffins, olefins, naphthenes &
aromatics. The catalytically derived liquid fraction showed good
agreement in fuel properties with the standard diesel fuel; hence
Please cite this article in press as: I. Ahmad, et al., Valorization of spent lubricant engine oil via catalytic pyrolysis: Influence of barium-
strontium ferrite on product distribution and composition, J. Anal. Appl. Pyrol. (2016), http://dx.doi.org/10.1016/j.jaap.2016.10.008
Catalyzed Run Standard ASTM Values
0.89 0.85
0.89 0.85
27.49 39–44 (typical 40)
B.D 0.01
2.00 1.3–4.1
<−6 −35 to −15
183.2 (84 ◦ C) 154
50.62 47
46.45 40–55
43 42–44
it could be used as a potential candidate for use in commercial
applications as substitute to diesel fuel.
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