Journal of Analytical and Applied Pyrolysis 134 (2018) 150–161

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Journal of Analytical and Applied Pyrolysis

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

Waste and virgin high-density poly(ethylene) into renewable hydrocarbons T

fuel by pyrolysis-catalytic cracking with a CoCO3 catalyst
Man Vir Singh
Department of Chemistry, Banasthali Vidyapith, Rajasthan, India

A R T I C LE I N FO A B S T R A C T

Keywords: Conversion of waste and virgin high-density poly(ethylene) (HD-PE) into renewable fuel/petrochemicals were
HD-PE carried out using a basic cobalt carbonate (CoCO3) catalysts by a pyrolysis-catalytic cracking process. The
Pyrolysis-catalytic cracking pyrolysis-catalytic cracking process provides an alternative clean fuel and also minimizes to the environmental
Renewable hydrocarbons problems by waste plastics. Renewable hydrocarbons fuel were analyzed by 2D-GC × GC/TOFMS, FT-IR spec-
CoCO3 catalysts
troscopy, 1H NMR spectroscopy, CHNS/O analyzer, inductively coupled plasma (ICP) and its results found ab-
2D-GCxGC/TOFMS
solutely good hydrocarbon compounds as (in fuel were petrochemicals obtained from virgin plastic and waste
HD-PE). Catalytic conversion rates of four experiments as virgin HD-PE into renewable hydrocarbons fuel was
found 80%, 84.40%, 88.22%, 92%, light gases 19.69%, 15.35%, 11.53%, 7.77%, residues 0.31%, 0.28%, 0.25%,
0.30 recovered from the overall production. Catalytic conversion rates of four experiments as waste HD-PE into
renewable hydrocarbons fuel was found 79%, 82%, 84%, 91%, light gases 20.50%, 17.55%, 15.65%, 8.59%,
residues 0.50%, 0.49%, 0.35%, 0.41. Renewable hydrocarbon fuel was analyzed using ICP for sulfur contents, it
was found very low sulfur content than ordinary fuel. It was observed that it is the only degradation of virgin and
waste HD-PE but not creating any other reactions.

1. Introduction
Plastic products are used for various purposes because of wide ap-
plications of plastic such as lightweight, high durability, sustainability,
design flexibility, a faster rate of manufacturing and resistant to che-
micals and moistures [1–3]. Therefore, plastic production has also in-
creased in globally over fifty years. In 2016 global plastic production is
estimated to have been some 311 million tons, up from 269 million tons
in 2014-15 [4,43], with the plastics market projected to have a value of
654 billion US-dollars by 2020 [5]. In 2000, total plastics production
was 160 million tons in the world. In 2010, total plastics production
was 300 million tons. It is likely to reach over 530 million tons in 2020
[6], the largest growth, in particular has been specifically in packaging
which accounts for more than half of the projected 2020 market value
(375 billion US dollars) [7]. Global plastic solid waste production has
continued to increase to its present value of 150 million tons per year
[3]. Especially the oceans with an estimated 8 million tones of plastic
being disposed of in the world’s oceans every year [8], waste of plastics
is continuously increasing because of the loss of natural resources [9].
High durability of plastics causes the great threat to the environment
system and its results from landfill, the release of toxic gasses like CO,
CO2, SO2, NOx and contributes to the global warming [10,11]. Further,
the dumped waste plastics are also causing risk of the environment,
human health and public amenities [12]. Recycled plastics are sig-
nificantly cheaper than virgin plastics [3], Feedstock recycling, which
turned plastics waste into valuable chemicals fuels by chemical re-
cycling method, has been considered cost-effectively and environment-
friendly method for minimize the consequences of plastics. Pyrolysis-
catalytic cracking which is a plastic recycling technique which when
used with the appropriate catalyst can have the ability to regulate
product yield [13,3]. These catalysts includes, Lin et al. used FCC, ZSM-
5 catalyst for waste polymer [14], Shah et al. used catalyst CaC2, alu-
mina, MgOH, ZnO, and heterogeneous mixture of silica and alumina for
low density polyethylene plastic [15], Tang et al. used catalyst Al-Zn
composite for polypropylene plastic [16], Saha et al. used catalyst
mesoporous (Al-MCM-41) for polypropylene plastic [17], Muhammad
et al. used catalyst to sulfates modified zirconium for high-density
polyethylene plastic [18], Zhou et al. used catalyst for low-density
polyethylene plastic [19]. Singh et al. used CuCO3 catalyst for waste
HD-PE [20]. According to 2D GCxGC/TOFMS, the identification of
hydrocarbon compounds in crude oil is great importance to the petro-
chemical industry, knowledge of the composition of crude oils, pyr-
olysis oil, and product quality assessment. Mass spectrometers that are
usually used as a confirmation tool only require a higher degree of
analytical skill, chromatographic separation to avoid misinterpretation
of the spectrum generated. The 2D GCxGC/TOFMS offers various

E-mail address: manvir25365@gmail.com.

https://doi.org/10.1016/j.jaap.2018.06.003
Received 1 May 2018; Received in revised form 20 May 2018; Accepted 1 June 2018
Available online 12 June 2018
0165-2370/ © 2018 Elsevier B.V. All rights reserved.
M.V. Singh
advantages over other types of GC–MS systems, spectral collection rates
up to 500 full-range mass spectra per second (500 Hz) only MS detector
competent of accurate comprehensive multi-dimension chromato-
graphy [21–32]. 2D GCxGC/TOFMS is one of the quick and high-re-
solution systems available for separation of volatile and semi volatile
organic chemicals, which can be utilized in the identification unknown
compounds [33]. The aim of present research was the conversion of
virgin and waste HD-PE plastics into renewable hydrocarbons (petro-
chemicals) using a cobalt carbonate (CoCO3) catalysts that could be
used as petrol/diesel. Higher rate of conversion in renewable fuel at the
lower levels of temperature was very important. A pyrolysis-catalytic
cracking process provides alternate of virgin and waste HD-PE plastics
which is cost effective and sustainable.
2. Materials and method
2.1. Materials
Waste high-density poly(ethylene) collected from local markets
(Jhunjhunu, Rajasthan, India), and shorted by locking for the Society of
Plastic Industry (SPI) code 2, its density was 0.965 g/cm3. Virgin HD-PE
granules were purchased from a supplier. Waste HD-PE was washed
with liquid soap making it entirely dust free and then dried in the
presence of sunlight. Waste water was treated by dilute solutions of
acidic (5% HCl) and alkali (5% NaOH). Wastes HD-PE plastic was
grounded to less than 5–6 mm2 pieces using grinder machine. These
grounded wastes were placed into the borocil glass reactor before the
experiment process.
2.2. Experimental
Virgin HD-PE plastic pieces < 3-4 mm2 (100%, 98%, 95%, 90%)
was mixed with weight percent/gram of (0%, 2%, 5% and 10%) CoCO3
[Central Drug House (CDH) New Delhi, India] catalyst, waste HD-PE
(100%, 98%, 95%, 90%) with different weight percent/gram of (0%,
2%, 5% and 10%) cobalt carbonate (CaCO3) catalyst, simply blended
materials before experiments were separately placed into a Borosil glass
reactor. The glass reactor has inside the diameter 160 mm, height was
158 mm, neck of reactor length was 300 mm and wall thickness of re-
actor was 3 mm. After that round shape the glass reactor (Fig. 1) was
placed in an insulated furnace which has a temperature controller and
digital energy meter. The heat temperature of furnace is regulated
through an electronic temperature regulator that maintains the
Fig. 1. the pyrolysis production diagram for turning waste and virgin HD-PE into renewable hydrocarbon fuel [20].
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Journal of Analytical and Applied Pyrolysis 134 (2018) 150–161
temperature at a specific time and closes the temperature in the right
set conditions. Pyrolysis process was started at 21 °C to reach 395 °C; it
was achieved within 17 min with 19 °C/m heating rate. Coil condenser
unit was set up with the glass reactor, also alternative finish with the
fuel collection device. Total run time of pyrolysis experiment was 4 h
20 min. The solid virgin and waste plastic had melted and their carbon
chain cracked into the vapors (fragment with lower molecular weight)
inside the glass reactor and after that passed from beginning to end a
reactor neck to a condenser then obtained in liquid as renewable or-
ganic compounds/petrochemicals, gases, residues.
2.3. Analytical methods
The functional group of renewable hydrocarbon fuels from waste
and virgin HDePE plastics and also raw waste and virgin HDePE were
determined using Fourier-transform infrared (FT-IR) spectrometry with
an Alpha-T spec-trometry (Bruker). A TGA 4000 thermo-gravimetric
analyzer (Perkin Elmer) was used to investigate the thermal stability of
waste and virgin HDePE using time and temperature. Leco pegasus 4D
model 2D-GC × GC/TOFMS has been applied for chemical analysis of
the renewable hydrocarbon fuel, analytical methods more described in
Man Vir Singh et al. [20]. Every 1H NMR spectra were recorded on a
Agilent DD2 500 MHz FT-NMR spectrometer operating at the proton
frequency of 500 MHz, spectral width 7512 Hz (-2.5–12.5 ppm), 90°
pulse = 10.7 μs, relaxation delay = 20 s, digital resolution 0.49 Hz/
point. 32 repetitions were averaged with 32 K data point and 6.38 min
run time. Renewable hydrocarbon fuels from found waste and virgin
plastics were analyzed by an elemental analyzer (Perkin-Elmer series-II
CHNS/O 24,000). TAN and TBN values of renewable hydrocarbons
were measured by ASTM D 664 and ASTM D 2896. Ash content, RBCR
and copper strip corrosion for 3 h at 100 °C temperature in renewable
hydrocarbons samples, which are prescribed by IS 1448 (P4) 2008, IS
1448 (P8) 2008, IS 1448 (P15) 2004, ISO 2160:1998 test methods.
Flash and fire point were measured by IS 1448 (P20) 2007 method.
Kinematic Viscosity at 40 and 100 °C measured by ASTM D 445. Density
calculated by hydrometer of IS 1448 (P32) 2008 methods. Sulfur con-
tent is measured by ASTM D 5185. Chlorine contents are measured by
ASTM D 808-05 test method. Initial and final boiling points are mea-
sured by ASTM D86 test method. Water contents in renewable hydro-
carbons fuel is measured by ASTM D1744 test method. Particle counter
in renewable hydrocarbons fuel is measured by ISO 4406. Inductively
coupled plasma (ICP) (Spectro GENESIS OES model) was used for metal
detection in renewable hydrocarbon fuel. Nitrogen
M.V. Singh Journal of Analytical and Applied Pyrolysis 134 (2018) 150–161

Table 1
Functional groups of waste and virgin. HD-PE.
Reported Observed Functional groups
Wavenumber−1 Wavenumber−1

2914.44 2914 Methyl (eCH3) asym./

sym. stretch
2846.93 2846 OeCH3, CeH stretch
1462.04, 1471.89 1462, 1471 Methylene CeH bend
1016.49 1016 Primary amine, CeN
stretch
719.45 719 1,3 disubstitution (ortho)

Table 2
Proximate and ultimate analysis of waste and virgin HD-PE [34].
Proximate analysis

Properties Waste HD-PE (%) Virgin HD-PE (%)

Fig. 2. Pre-analyses of waste and virgin HD-PE using TGA. Moisture 00 00

Volatile matter 100 100
Fixed carbon 00 00
adsorption–desorption determine was performed at liquid N2 analysis Ash contents 00 00
gas with a Quantachrome Asiqwin™. The sample was outgas at 300 C for Ultimate analysis
3.4 h, at 6.58e-05 1/Torr. Final analysis time was 6 h 31 min and bath Carbon 80.58 84.95
temperature was 77.35 K. The cold zone and warm zone were Hydrogen 13.98 14.30
1.18408cc, 7.86017cc. The isotherm was used to determine specific Nitrogen 0.60 0.55
Sulfur 0.080 –
surface area by BET equation.
Oxygen and other 5.19 0.20
Chlorine – –
CGV (Mj/Kg) 45.78 –
3. Results and discussion

3.1. Analyzed of waste and virgin HD-PE plastics for pyrolysis feedstock
3.2. Mass recoveries of gases, renewable liquids and residues from waste
and virgin HD-PE
Waste and virgin HD-PE was pre-analyzed by TGA as shown in
Fig. 2. Heat range of virgin HD-PE degradation was 30 °C–475 °C and
Recoveries of gases, renewable hydrocarbons and residues from
waste HD-PE degradation was 30 °C–510 °C at 20 °C per minutes. This
virgin HD-PE were obtained; it is shown in Fig. 4. Virgin HD-PE (100,
will be useful for investigating the thermal stability of waste and virgin
98, 95, 90 g) with different weight percent of (0%, 2%, 5%, 10%) cobalt
plastic for pyrolysis process.
carbonate (CoCO3) catalyst whose rate of conversion were 19.69%,
The FT-IR spectra of waste and virgin HD-PE plastics are shown in
15.35%, 11.35% and 7.77% light gases, 80%, 84.40%, 88.22% and 92%
Fig. 3 and its functional groups are shown in Table 1. Collected some
in renewable hydrocarbons fuel and 0.31%, 0.25%, 0.43% and 0.23
functional groups are similar from waste and virgin HD-PE plastics. All
residues. Obtain renewable hydrocarbon fuel from virgin HD-PE was
functional groups were hydrocarbons; therefore, it could be converted
analyzed by an elemental analyzer. A renewable hydrocarbon fuel from
to renewable hydrocarbons fuel.
virgin HD-PE was consisting of carbon 88.20%, Hydrogen 9.87% and
Proximate and ultimate analyses of waste and virgin HD-PE have
Nitrogen 0.04%.
been shown in Table 2. Volatile matter was 100% in the proximate
Recoveries of gases, renewable hydrocarbons and residues from
analysis because of absence of ash in waste and virgin HD-PE. Oxygen
waste HD-PE were obtained; it is shown in Fig. 5. Waste HD-PE (100,
was 5.19% in waste HD-PE because of the added some additives during
98, 95, 90 g) with different weight percent of (0%, 2%, 5%, 10%) cobalt
manufacturing of plastic products.
carbonate (CoCO3) catalyst whose rate of conversion in renewable
hydrocarbons fuel were 79%, 82%, 84%, 91%, light gases 20.50%,
17.55%, 15.65%, 8.59%, and residues 0.50%, 0.49%, 0.35%, 0.41.
Total 12% yields increased when the catalyst increased from 2% to 10%
with waste and virgin HD-PE than without catalyst yield which has less.
CoCO3 catalyst worked similar with both types of plastics. A renewable
hydrocarbon from waste HD-PE was consisting of carbon 88.0%, Hy-
drogen 11.67% and Nitrogen 0.06%. Calorific value directly connected
to carbon content of hydrocarbon, renewable hydrocarbon fuel con-
sisted of high carbon and hydrogen contents; therefore, definitely ca-
lorific value will be higher (Table 3).

3.3. Renewable hydrocarbons properties of petrol/diesel fractions

All properties of renewable hydrocarbons from waste and virgin

HD-PE and results of this are shown in Table 4, and were found
equivalent to ordinary petrol/diesel; therefore, it is suitable for petrol/
diesel engines. TAN and TBN properties of renewable hydrocarbons
Fig. 3. Pre-analyses of waste and virgin HD-PE using FT-IR. from HD-PE were 2.02 mg KOH/g and 0.32 mg KOH/g. Ash content,

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Fig. 4. Fractions obtained from virgin HD-PE.

RBCR and copper strip corrosion for 3 h at 100 °C in renewable hy-
drocarbons samples were values found equivalent to ordinary petrol/
diesel. Flash and fire point were less slightly higher to IS 1460–2005
test method. Kinematic Viscosity at 40 °C and 100 °C were results found
1.80 and 1.05. Density calculated by hydrometer was equivalent to
ordinary diesel. Sulfur content is lower than ordinary petrol/diesel but
chlorine contents are absence. Initial and final boiling point is equiva-
lent to ordinary petrol/diesel. Renewable hydrocarbons fuel avoids the
need of further upgrading and low sulfur contents in renewable hy-
drocarbon fuel make the very high calorific value and prevent SO2
environment pollution. Renewable fuel can be used as the different
purpose of energy-source like petrol/diesel engines.
Renewable hydrocarbon fuel from waste and virgin HD-PE was
characterized using with ICP for metals detective as shown in Table 5,
are found less than ordinary petrol/diesel.
3.4. Properties of cobalt carbonate (CoCO3) catalyst
The physical properties of the cobalt carbonate (CoCO3) catalyst
were investigated with SEM. It was observed that a ordinary diameter
of 2.8 μm, a ordinary length 7 μm, a ordinary width 1.3 μm and a or-
dinary diameter 25 μm [39]. Langmuir isotherm is I type because it
depicts monolayer nitrogen gas adsorption energy (Fig. 6c). Isotherm of
I type is received when P/P0 < 1 and c > 1 in the BET equation, where
P/P0 partial pressure and c is BET constant, microporous CoCO3 catalyst
with pore diameter less than 2 nm. The isotherm data collected from
multi-point BET plot (Fig. 6a) at the P/P0 pressure range 0.05 to 0.3.
The surface area of CoCO3 catalyst is 103.667 m2/g, if higher the sur-
face area more will be cracking.
3.5. Mechanism of HD-PE
The basic CoCO3 catalyst plays important role in pyrolysis method.
The depolymerization of virgin and waste HD-PE using CoCO3 also
occurred via a carbenium ion mechanism and the hydrocarbons pro-
ducts of the β-scission were received. CoCO3 cleavage into CoO com-
pound being there of heat in a reactor, CoO basic sites may produce
components of HD-PE depolymerize via a carbenium mechanism that
caused an increase in the quantity of olefins by the β-scission reaction.
Depolymerization of HD-PE plastic over CoCO3 catalyst, once carbanion
(low molecular weight hydrocarbons) came in contact with one another
to make cyclic or aromatics high molecular weight hydrocarbons, me-
chanism more explained by Singh et al. [20].
3.6. Chemically compare of renewable hydrocarbons from waste and virgin
HD-PEx
Obtained renewable hydrocarbon fuel from virgin HD-PE plastic,
2D-GCxGC/TOFMS spectra (Chroma-TOF software also offers a fully
automated) shown in Fig. 8 that is different types of hydrocarbon

Fig. 5. Fractions obtained from waste HD-PE.

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Table 3
comparison of gases, liquids and residues from plastics.
Plastics Catalyst Temperature Gases (%) Liquids (%) Residues (%) References

Waste HD-PE CuCO3 (2 %) 23-390 9.66 90 0.34 [20]

Waste HD-PE CuCO3 (5 %) 23-390 5.64 94 0.36 [20]
Waste HD-PE CuCO3 (8 %) 23-390 7.45 92 0.55 [20]
Virgin LD-PE – 420-460 14.23 84.30 1.47 [35]
Waste LD-PE – 420-460 15.60 77.07 7.33 [35]
Virgin PP – 420-460 13.67 84.83 1.50 [35]
Waste PP – 420-460 15.01 77.07 7.33 [35]
HD-PE HZSM-5 HY 500 – 58-70 – [36]
Waste HD-PE Ni/Z 450 68.27 30.74 1.10 [37]
HD-PE-2 HZSM-5 370-420 5 90 5 [38]

Table 4 cyclic hydrocarbons (Bicyclo[3.1.1]heptan-3-one, 2,6,6-trimethyl-,

renewable hydrocarbons fuel from waste and virgin HD-PE analyzed by dif- (1à,2á,5à)-, Cyclohexane, 1-methyl-2-propyl-, 1,12-Tridecadiene) was
ferent parameters of petrol/diesel. 56.606%, aromatics hydrocarbons (Benzene, 1-methyl-2-(2-propenyl)-,
Parameters Requirements as per IS Results Benzene, 2-ethyl-1,4-dimethyl-) was 11.822%, phenanthrene hydro-
1460-2005 carbons (4-Phenanthrenol, 1,2,3,4-tetrahydro-4-methyl-, Anthracene,
9,10-dihydro-9,10-dimethyl-) was 0.303% and unclassified hydro-
TAN Not Specified 2.02 mg KOH/g
carbon was 20.822%, all appeared in the analysis result index (Table 7).
TBN Not Specified 0.32 mg KOH/g
Ash content 0.01 Max 0.002 % by weight
Chemical composition of renewable hydrocarbon from virgin and waste
RBCR (On 10% Residue) 0.30 Max 0.021 % by weight HD-PE both are found closely similar.
Copper Strip Corrosion For Not worse than No.1 1a
3 h at 100 °C
Flash point 35 Min 37 °C
3.7. Chemical composition of renewable hydrocarbon
Fire Point 50 Min 52 °C
Kinematic Viscosity at 40 °C Not Specified 1.80 cSt
Kinematic Viscosity at 100 °C Not Specified 1.05 cSt To further investigate the renewable hydrocarbon fuel obtained
Density at 15 °C 820 to 890 88 g/ml from the depolymerization of virgin HD-PE using a CoCO3 catalyst was
Sulfur Content BSIII : 350 Max BSIV : 50 22.812 ppm analyzed by 2D-GCxGC/TOFMS. 2D-GCxGC chromatograms were vi-
Max
Water Content BSIII : NS BSIV : 200 Max 644 ppm
sualized in typically one-dimension version, two-dimension version
Particle Counter Not Specified 7 (contour plot) and three-dimension image (surface plot), as shown in
Particle Counter Not Specified 9 Fig. 8. The contour plot of GC × GC chromatogram conventionally
Chlorine Content NS NIL % by weight demonstrates the benefit of two-dimensional gas chromatography
Initial Boiling Point 131 °C
structured chromatogram. Table 6 reveals that degradation of waste
Final Boiling Point 316 °C
Moisture Less than 500 PPM 365 ppm plastics with pyrolysis catalytic degradation gave off maximum che-
mical products. As observed according to Table 6, obtained very less
amount of oxygenated, related sulfur compound than fossil fuel,
compounds (mono, di and poly-aromatics, paraffin’s, cyclo-hydro- therefore, not further more upgrading. Chemical composition of re-
carbons are shown 7A) were available in renewable hydrocarbon fuel newable hydrocarbon fuel from virgin HD-PE plastic comprised of
such as paraffin’s hydrocarbons (few example Decane, trans-3-Decene, paraffin’s hydrocarbons range C10-C25 7.635%, branched/cyclic
Undecane) was 7.635%, branched/cyclic hydrocarbons (few example 52.41%, aromatics (benzene, Nepthalines) 13.677%, phenanthrene
Benzene,1,2,3-trimethyl-, Benzene, 2-Cyclohexane-1-one, 2-methyl-, 0.41% and unclassified hydrocarbon 27.111%. According to the re-
Cyclopentene) was 52.41%, aromatics hydrocarbons (benzene, Nep- tention time (RT) and signal/noise (S/N) numbers petrochemicals as
thalines) was 13.677%, phenanthrene hydrocarbons was 0.41% and follow such as at the initial phase of the analysis at retention time
unclassified hydrocarbon was 27.111%, all appeared in the analysis (primary and secondary column) RT 456, 1.000 and S/N 1464 com-
result index (Table 6). It shows the various types of group in the definite pound is Benzene, 1,3-dimethyl-, RT 536, 1.030 and S/N 2529.4 com-
area of then two-dimension plan as an example mono, di, and poly- pound is Benzene, 1-ethyl-3-methyl-, RT 540, 1.120 and S/N 2272.9
aromatics, paraffin’s, cyclo-hydrocarbons. Collected (Fig. 10) renew- compound is Benzaldehyde, RT 548, 0.960 and S/N 2414.9 compound
able hydrocarbon fuel from waste HD-PE plastic 2D-GCxGC/TOFMS is E-1,6-undecadience, RT 548, 1.160 and S/N 1698.9 compound is
spectra shows that is different types of petrochemicals were available in 4(1 H)-Pyrimidinone, 6-methyl-, RT 556, 0.950 and S/N 9648.8 com-
renewable hydrocarbon fuel (Fig. 7B) such as saturated hydrocarbons pound is Aziridine, 1-propyl-, RT 556, 0.990 and S/N 2612.3 compound
(few examples, Nonane, Decene, Undecane) was 10.442%, branched/ is unknown 1, RT 556, 1.050 and S/N 5277 compound is Benzene, 1-
ethyl-2methyl-, RT 5600.940 and S/N 10,899 compound is Decane, RT

Table 5
Elemental reports of renewable hydrocarbon fuel (in PPM) from waste and virgin HD-PE.
S Cu Ca K Na Zn Cd Cr Mg Fe Si Al B Ti V Ni Mn Mo Sn P Pb Ba Ag

Renewable hydrocarbon fuel from waste

22.812 0.008 0.013 0.854 1.154 0.113 0.003 0.008 00 0.010 0.053 0.242 2.439 0.004 0.017 0.014 0.001 0.032 0.073 2.357 0.161 00 0.016

Renewable hydrocarbon fuel from virgin

2.819 0.007 0.012 0.837 1.416 0.050 0.003 0.007 00 0.010 0.052 0.247 0.3.189 0.004 0.017 0.014 0.001 0.031 0.072 5.527 0.157 00 0.016

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M.V. Singh
Table 6
Chemical composition of renewable liquid from virgin HD-PE.
Name of Compounds
Benzene, 1,3-dimethyl-
Benzene, 1-ethyl-3-methyl-
Benzaldehyde
E-1,6-Undecadiene
4(1 H)-Pyrimidinone, 6-methyl-
Aziridine, 1-propyl-
Unknown 1
Benzene, 1-ethyl-2-methyl-
Decane
trans-3-Decene
5-Cyano-1-pentene
1H-Fluorene, dodecahydro-
Benzene, 1,2,3-trimethyl-
Benzene, 1-ethenyl-3-methyl-
1,6-Octadiene, 3,7-dimethyl-
1,12-Tridecadiene
o-Cymene
Benzene, 1,2,3-trimethyl-
Cyclodecane
3,4-Octadiene, 7-methyl-
Undecane, 6-methyl-
Benzene, cyclopropyl-
Journal of Analytical and Applied Pyrolysis 134 (2018) 150–161
Fig. 6. (a) multi-point BET of CoCO3, (b) Isothermal of CoCO3, and (c) Langmuir of CoCO3.
Name of Compounds Name of Compounds Name of Compounds
Cyclohexane, 2-butyl-1,1,3-trimethyl- Naphthalene, 2-ethyl- Heptadecane, 3-methyl-
Bicyclo[3.1.1]hept-2-ene-2-ethanol, 6,6- Pentadecane Cyclohexane, undecyl-
dimethyl-
Benzene, hexyl- Unknown 43 9H-Fluorene, 1-methyl-
Naphthalene, 1,2,3,4-tetrahydro-1,4-dimethyl- 7-Pentadecyne Unknown 71
1H-Indene, 2,3-dihydro-4,7-dimethyl- Unknown 44 (3-Methylphenyl) methanol, n-pentyl
ether
7-Tetradecyne 2-Ethyl-3-methylene-indan-1-one Azulene, 1,4-dimethyl-7-(1-
methylethyl)-
1,8,11,14-Heptadecatetraene, (Z,Z,Z)- Cyclopentadecane Fluorene, 4-[1,2-dihydroxyethyl]-
Unknown 17 Aromandendrene Unknown 72
Benzene, (1-methylpentyl)- 1,1'-Biphenyl, 4-methyl- 1-Octadecene
1H-Indene, 1,1-dimethyl- Heneicosane Benzene, undecyl-
2-Pentadecyn-1-ol Cyclooctane, 1,4-dimethyl-, trans- 5-Tridecene, (Z)-
1,7,7-Trimethyl-2-vinylbicyclo[2.2.1]hept-2- 7-Pentadecyne Octadecane
ene
1H-Indene, 2,3-dihydro-1,6-dimethyl- Tetradecane, 1-iodo- Benzene, (1-methyldecyl)-
Unknown 18 Naphthalene, 1-propyl- Bis(2-methoxyethyl) phthalate
Tridecane 1,1'-Biphenyl, 4-methyl- E-2-Octadecadecen-1-ol
Unknown 19 1H-3a,7-Methanoazulene, octahydro-1,4,9,9- E-7-Octadecene
tetramethyl-
Anisole, o-(1-ethylvinyl)- Benzene, (1-methyl-1-propylpentyl)- Unknown 73
Naphthalene, 1,2,3,4-tetrahydro-1,1-dimethyl- Acenaphthene Unknown 74
Oleyl alcohol, trifluoroacetate Cyclopentadecane Trans-1-methyl-2-nonyl-cyclohexane
Unknown 20 Naphthalene, 1,4,5-trimethyl- Tridecane, 5-propyl-
Bicyclo[4.1.0]heptane, 3-methyl-7-pentyl- Pentadecane cis-2-Methyl-7-octadecene
1-Methyl-2-n-hexylbenzene Unknown 45 Phenanthrene
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M.V. Singh Journal of Analytical and Applied Pyrolysis 134 (2018) 150–161

Fig. 7. A renewable liquid from virgin HD-PE, 7 B renewable liquid from waste HD-PE.

Fig. 8. A counter plot of GC × GC chromatogram, B surface plot, C counter plot with labeled groups.

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M.V. Singh Journal of Analytical and Applied Pyrolysis 134 (2018) 150–161

Table 7
Chemical composition of renewable liquid from waste HD-PE.
Name of Compounds Name of Compounds Name of Compounds Name of Compounds

Name Cyclododecene, 1-methyl- Heptadecane Unknown 65

Nonane Naphthalene, 5-ethyl-1,2,3,4- Unknown 90 Cyclopropane, 1,1,2,2-tetramethyl-3-(2-
tetrahydro- phenylethenylideno)-
Decane Decane, 4-ethyl- 1-Docosene Naphthalene, 1,2,3,4-tetramethyl-
Undecane 1,Z-5,E-7-Dodecatriene Heptadecane Benzene, tridecyl-
Tridecane 3-Octene, 2,2-dimethyl- Unknown 91 Benzene, (1-methyldodecyl)-
Tetradecane Unknown 22 1-Iodo-2-methylundecane Benzene, 1,2,3-trimethyl-
Pentadecane 3,5-Dodecadiyne, 2-methyl- Cyclohexane, (2-methylpropyl)- Unknown 86
Hexadecane Cyclooctane, 1,4-dimethyl-, cis- Cyclopentane, 1,1'-ethylidenebis- Benzene, 1-methyl-3-hexyl-
Heptadecane Bicyclo[6.1.0]nonane, 9-(1- 9-Tricosene, (Z)- Unknown 87
methylethylidene)-
Octadecane 4-Tetradecyne 1-Docosene Benzene, tetradecyl-
Nonadecane Benzene, 1-methyl-3-hexyl- Tetradecane, 1-iodo- 5,9-Tetradecadiyne
Eicosane Unknown 23 Cyclohexane, 1-isopropyl-1-methyl- Benzene, 1-methyl-3-hexyl-
Heneicosane Tridecane, 3-methyl- Benzene, propyl- Unknown 89
Docosane Unknown 24 Benzene, 1-ethyl-2-methyl- Benzene, pentadecyl-
Tricosane Unknown 25 Benzaldehyde Benzene, (1,3-dimethylbutyl)-
Tetracosane Unknown 26 Benzene, 1-ethyl-2-methyl- Benzene, 1-methyl-3-hexyl-
Pentacosane (E,Z,Z)-2,4,7-Tridecatrienal Benzene, 2-propenyl- Benzene, hexadecyl-
Phenanthrene 3-Tetradecene, (Z)- Benzene, 1,2,3-trimethyl- Ethylbenzene
4-Phenanthrenol, 1,2,3,4-tetrahydro-4- 1,13-Tetradecadiene Benzene, (1-methylpropyl)- p-Xylene
methyl-
Unknown 77 Cyclotetradecane Benzene, 1-methyl-2-(1-methylethyl)- 1,3,5-Cycloheptatriene, 7,7-dimethyl-
9-Phenanthrenol 1,13-Tetradecadiene Benzene, 1-ethyl-4-methyl- 4-Decyne
9H-Fluorene, 9,9-dimethyl- 1-Octanol, 2-butyl- Benzene, 2-ethyl-1,3-dimethyl- 1-Decene
Anthracene, 9,10-dihydro-9,10- 7-Tetradecyne Benzene, 1-ethenyl-2-methyl- Cyclooctane, ethenyl-
dimethyl-
9H-Fluorene, 9,9-dimethyl- Cyclohexene, 1-octyl- Bicyclo[3.2.1]oct-2-ene, 3-methyl-4- 1-Decene
methylene-
5H-Dibenzo[a,d]cycloheptene, 5- Benzene, (1-methyl-1-propylpentyl)- Indene Borane, ethylisopropylmethyl-
methylene-
Phenanthrene, 1-methyl- Cyclopentadecane Ethanone, 1-(2-methylphenyl)- Cyclohexane, 1-methyl-2-propyl-
5H-Dibenzo[a,c]cyclohepten-5-ol Decane Benzene, 1-methyl-2-(2-propenyl)- Dihydromyrcene

564, 0.960 and S/N 1533.4 compound is trans-3-Decene, RT 564, 0.970
and S/N 2386.3 compound is 5- Cyano-1-pentene, RT 5640.980 and S/
N 1175.3 compound is 1H-Fluorence, dodecahydro-, respectively.
Fig. 9 is shown the 1H NMR spectrum of renewable hydrocarbons
from virgin HD-PE plastics, different resonance signals to various
groups have been indicated in the spectrum. Aromatic ring 1H (protons)
region 6.5–9.0 ppm, α-alkyl CH2, CH3, 2.0–3.5 ppm βeCH and CH2
group to aromatic ring and eCH and CH2 groups of cycloalkanes and
normal isoparaffins region 1.0–2.0 ppm and eCH3 of branched and
normal paraffins region 0.5–1.0 ppm. Aromatics is 11.9%, olefins is
57.8% saturates is 30.3% and hydrogen content 13.3% contents have
been estimated by 1H NMR method as described by Bansal et al.

Fig. 9. 1H NMR spectrum of renewable hydrocarbons from virgin HD-PE.

157
M.V. Singh
Fig. 10. A counter plot of GC × GC chromatogram, B surface plot, C counter plot with labeled groups.
[40–42].
To further investigate of the renewable hydrocarbon fuel obtained
from the degradation of waste HD-PE plastic using a CoCO3 catalyst was
analyzed by (See Fig. 10 and Table 7) 2D-GCxGC/TOFMS. The tech-
nology of 2-D gas chromatography has developed speedily been applied
in the liquid hydrocarbon fuel. The contour plot of GC × GC chroma-
togram typically demonstrates an advantage of 2D-GC structured
chromatogram. Chemical composition of renewable hydrocarbon fuel
from waste HD-PE plastic comprised of paraffin’s hydrocarbons range
C9-C25 10.442%, branched/cyclic 56.60%, aromatics (benzene, Nep-
thalines) 11.822%, phenanthrene 0.30% and unclassified hydrocarbon
20.822%. According to the retention time (RT) and signal/noise (S/N)
numbers petrochemicals as following such as at the preliminary stage of
the analysis at retention time (primary with secondary column) RT 476,
0.920 and S/N 5185.7 compound is Nonane, RT 560, 0.950 and S/N
158
Journal of Analytical and Applied Pyrolysis 134 (2018) 150–161
13585 compound is Dacane, RT 1036, 1.040 and S/N 16632 compound
is Hexadecane, RT 1192, 1.400 and S/N 3434.1 compound is 4-Phe-
nanthrenol, 1,2,3,4-tetrahydro-4-methyl-, RT 1212, 1.500 and S/N
1389.7 compound is 9-Phenanthrenol, RT 592, 0.980 and S/N 2622.5
compound is E-1,6-Undecadiene, RT 608, 0.960 S/N 1503 compound is
Bicyclo[3.1.1]heptan-3-one, 2,6,6-trimethyl-, (1à,2á,5à)-, respectively.
GC × GC chromatogram of the (surface plot) against a one-dimension
version of the GC × GC chromatogram clearly shows that two dimen-
sional gas chromatography has good separation, the peaks crowded in
one-dimension were fine separated along the second dimension of the
two-dimension plane, and it also demonstrates further benefit of two
dimensional gas chromatography high sensitivity with providing bigger
peak ability.
Fig. 11 is shown the 1H NMR spectrum of renewable hydrocarbons
from waste HD-PE plastics, various resonance signals to different
M.V. Singh
Fig. 11. 1H NMR spectrum of renewable hydrocarbon from waste HD-PE.
groups have been marked in the spectrum. Aromatic ring 1H (protons)
region 6.5–8.5 ppm, α-alkyl CH2, CH3, 2.0–3.75 ppm βeCH and CH2
group to aromatic ring and eCH and CH2 groups of cycloalkanes and
normal isoparaffins region 1.0–2.0 ppm and −CH3 of branched and
normal paraffins region 0.5–1.0 ppm. Aromatics is 11.5%, olefins is
45.5% saturates is 43.0% and hydrogen content 13.3% contents have
been estimated by 1H NMR method.
4. Conclusion
Successful pyrolysis-catalytic conversion of waste and virgin HD-PE
into renewable hydrocarbon fuel was carried out during the process.
Waste HD-PE is very cheaper than virgin HD-PE. Chemical composition
of renewable hydrocarbon from virgin and waste HD-PE, thermal sta-
bility of virgin and waste HD-PE, functional groups of raw waste and
Appendix A
Figure 1H NMR spectrum of liquid hydrocarbons from standard HD-PE plastics.
159
Journal of Analytical and Applied Pyrolysis 134 (2018) 150–161
virgin HD-PE and 1H NMR, all are results of virgin and waste HD-PE
found closely similar, therefore, virgin and waste HD-PE can be used for
as a pyrolysis feedstock without any separation. 2D-GCxGC/TOFMS has
been utilized for the pyrolysis-catalytic degradation of waste and virgin
HD-PE plastics, it was found five groups of compounds including par-
affin’s, olefins, cyclic/branched, aromatics (benzenes, nephthalenes)
and phenanthrene, have been detected in the degradation of waste and
virgin HD-PE plastics. Carbon range was C10 to C25 in renewable hy-
drocarbon fuel from virgin HD-PE plastic and C9–C25 in fuel from waste
HD-PE plastic. Renewable hydrocarbon fuel from waste and virgin HD-
PE plastics were absolutely found that equal to petrol/diesel fuel. In
renewable hydrocarbons from waste and virgin HD-PE have been found
aromatics 11.5%, 11.9%, olefins 45.5%, 57.8% saturates 43.0%, 30.3%
and hydrogen contents 13.3%, 13.3% contents using 1H NMR.
M.V. Singh Journal of Analytical and Applied Pyrolysis 134 (2018) 150–161

NMR measurements

All proton NMR spectra were recorded on a Agilent DD2 500 MHz FT-NMR spectrometer operating at the proton frequency of 500 MHz, spectral
width 7512 Hz (−2.5–12.5 ppm), 90° pulse = 10.7 μs, relaxation delay = 20s, digital resolution 0.49 Hz/point. 32 repetitions were averaged with
32K data point and 6.38 min experimental time. All the NMR spectra were integrated after baseline correction, and a mean of minimum three
integration values has been taken for each calculation.
Above figure shown the 1H NMR spectrum of liquid hydrocarbons from standard HDPE plastics, various resonance signals to different groups
have been marked in the spectrum. Aromatic ring protons region 6.5–9.0 ppm, α-alkyl CH2, CH3, 2.0–3.5 ppm βeCH and CH2 group to aromatic ring
and eCH and CH2 groups of cycloalkanes and normal isoparaffins region 1.0–2.0 ppm and eCH3 of branched and normal paraffins region 0.5–1.0
ppm. Aromatics 11.9%, olefins 57.8% saturates 30.3% and hydrogen content 13.3% contents have been estimated by 1H NMR method as described
by Bansal et al. [41,42].

Above figure 4.1.3.9 shown the 1H NMR spectrum of liquid hydrocarbons from waste HDPE plastics, various resonance signals to different groups
have been marked in the spectrum. Aromatic ring protons region 6.5–8.5 ppm, α-alkyl CH2, CH3, 2.0–3.75 ppm β−CH and CH2 group to aromatic
ring and −CH and CH2 groups of cycloalkanes and normal isoparaffins region 1.0–2.0 ppm and −CH3 of branched and normal paraffins region
0.5–1.0 ppm. Aromatics 11.5%, olefins 45.5% saturates 43.0% and hydrogen content 13.3% contents have been estimated by 1H NMR method.

Appendix B. Supplementary data

Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.jaap.2018.06.003.

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