Fuel Processing Technology 122 (2014) 7990

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Fuel Processing Technology

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Production, characterization and fuel properties of alternative diesel fuel

from pyrolysis of waste plastic grocery bags
Brajendra K. Sharma a,, Bryan R. Moser b, Karl E. Vermillion b, Kenneth M. Doll b, Nandakishore Rajagopalan a
a
b

Illinois Sustainable Technology Center, Prairie Research Institute, University of Illinois, Urbana-Champaign, 1 Hazelwood Dr., Champaign, IL 61820, USA
United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, Peoria, IL 61604, USA

a r t i c l e

i n f o

Article history:
Received 3 October 2013
Received in revised form 11 January 2014
Accepted 18 January 2014
Available online 11 February 2014
Keywords:
Plastic
Pyrolysis
High-density polyethylene
Fuel
Diesel
Biodiesel

a b s t r a c t
Pyrolysis of HDPE waste grocery bags followed by distillation resulted in a liquid hydrocarbon mixture with
average structure consisting of saturated aliphatic parafnic hydrogens (96.8%), aliphatic olenic hydrogens
(2.6%) and aromatic hydrogens (0.6%) that corresponded to the boiling range of conventional petroleum diesel
fuel (#1 diesel 190290 C and #2 diesel 290340 C). Characterization of the liquid hydrocarbon mixture was
accomplished with gas chromatographymass spectroscopy, infrared and nuclear magnetic resonance spectroscopies, size exclusion chromatography, and simulated distillation. No oxygenated species such as carboxylic
acids, aldehydes, ethers, ketones, or alcohols were detected. Comparison of the fuel properties to the petrodiesel
fuel standards ASTM D975 and EN 590 revealed that the synthetic product was within all specications after
addition of antioxidants with the exception of density (802 kg/m3). Notably, the derived cetane number (73.4)
and lubricity (198 m, 60 C, ASTM D6890) represented signicant enhancements over those of conventional
petroleum diesel fuel. Other fuel properties included a kinematic viscosity (40 C) of 2.96 mm2/s, cloud point
of 4.7 C, ash point of 81.5 C, and energy content of 46.16 MJ/kg. In summary, liquid hydrocarbons with
appropriate boiling range produced from pyrolysis of waste plastic appear suitable as blend components for
conventional petroleum diesel fuel.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Plastic retail bags are ubiquitous in modern society because they represent a convenient means to transport purchased goods from the supermarket to the home. Plastic bags are plentiful, inexpensive to produce,
sturdy yet low weight, and easy to store and transport. However, the
same properties that make them commercially successful also contribute
to their proliferation in the environment. Although they are recyclable,
the U.S. EPA noted that only 13% of the approximately one trillion produced in 2009 were recycled in the U.S. [1]. The remainder were disposed
of in landlls, released into the environment as litter, or used in secondary
applications by end-users eventually ending in landlls. Plastic bags may
take centuries to naturally decompose due to their stable chemical composition [2]. In addition to being a source of litter in urbanized areas, plastic bags exacerbate localized ooding by clogging municipal drainage
systems and constitute a signicant portion of oating anthropogenic marine debris [35]. In fact, plastic bags contribute to the so-called Great Pacic Garbage Patch of oating refuse in the Pacic Ocean and have been

Disclaimer: Mention of trade names or commercial products in this publication is solely for the purpose of providing specic information and does not imply recommendation
or endorsement by the U.S. Department of Agriculture. USDA is an equal opportunity provider and employer.
Corresponding author.
E-mail address: bksharma@illinois.edu (B.K. Sharma).
0378-3820/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2014.01.019

detected as far north and south as the poles [35]. Once in the environment, plastic bags are lethal to animals that ingest or become entangled
in them [68]. Because of these and other factors, various regional and national governments have banned or are contemplating bans or fees on
plastic bags [9].
Standard plastic bags consist of thin polyethylene (PE) sheets
produced commercially from polymerization of ethylene. PE is divided
into categories based on density and molecular branching frequency.
The two types most important to production of plastic bags are lowdensity PE (LDPE) and high-density PE (HDPE). HDPE is a copolymer
with up to 1% 1-butene and is made historically with either Cr or Ziegler
catalysts at 116 MPa at temperatures as low as 60 C. More recently,
single site catalysts such as metallocenes have been employed [10].
LDPE is produced at high temperatures (200300 C) and supercritical
ethylene pressures (130260 MPa) using peroxide-free radical initiators [10]. HDPE is a linear copolymer with a density range of 0.945
0.965 g/cm3 whereas LDPE is branched with densities ranging from
0.915 to 0.925 g/cm3 [10]. Due to these differences in structure, the crystalline melting point, softening point and tensile strength of LDPE are
considerably lower than the corresponding values for HDPE [10]. However, LDPE shows higher elongation at break and higher impact strength
than does the more rigid HDPE [10]. It is also translucent rather than
opaque due its lower crystallinity (55%) relative to HDPE (8595%)
[10]. HDPE is more commonly utilized for production of plastic bags
due to its greater tensile strength coupled with its less energy-

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B.K. Sharma et al. / Fuel Processing Technology 122 (2014) 7990

Table 1
Fuel properties of pyrolyzed polyethylene hydrocarbons (PPEH) and ULSD along with a comparison to petrodiesel fuel standards.a
Units
Low temperature
CP
PP
CFPP
Oxidative stability:
IP, 110 C
OT
KV, 40 C
DCN
Flash point
Wear scar, 60 C
Sulfur
SG, 15 C
Density, 15 C
ST, 40 C
Moisture
HHV
a
b
c
d

ASTM D975b

EN 590

PPEH-L

PPEH-H

1:1 L/H

ULSD

c
c
c

c
c
c

30.1 (0.1)
37.3 (0.6)
31.0 (0)

4.7 (0.2)
4.0 (0)
3.7 (0.6)

5.9 (0.2)
8.3 (1.2)
6.0 (0)

17.5 (0.3)
20.3 (0.6)
16.0 (0)

c
c
1.94.1
40
52
520
15
c
c
c
c
c

20
c
2.04.5
51
55
460
10
c
820845
c
200
c

3.9 (0.3)/14.4 (0.8)d

175.2 (0.3)/186.9 (0.4)d
1.20 (0.01)
54.6 (1.1)
b30
293 (3)
3
0.777 (0.001)
776 (1)
22.5 (0.1)
106 (2)
45.86 (0.22)

12.9 (1.5)/N24d
190.1 (0.7)/202.1 (0.5)d
2.96 (0)
73.4 (1.4)
81.5 (0.7)
198 (10)
2
0.803 (0.001)
802 (0)
24.7 (0.1)
64 (3)
46.16 (0.09)

7.7 (0.9)/N24d
180.8 (0.5)/192.7 (0.6)d
2.08 (0)
66.3 (1.5)
90.3 (1.8)
282 (3)
2
0.792 (0.001)
791 (1)
23.6 (0.2)
84 (1)
46.04 (0.08)

N24
196.2 (0.5)
2.28 (0.01)
47.4 (0.9)
65.0 (0.7)
581 (5)
8
0.841 (0.001)
840 (1)
25.1 (0.2)
49 (3)
45.15 (0.19)

h
C
mm2/s
C
m
ppm
kg/m3
mN/m
ppm
MJ/kg

Values in parentheses represent standard deviations from the reported means (n = 3). For ash point, n = 1.
For No. 2 grade S15 (15 ppm S) ULSD.
Not specied.
With 1000 ppm BHT added.

intensive production process. Pyrolysis is dened as the irreversible anaerobic thermochemical decomposition of material at elevated temperature (300+ C). The principal benet of pyrolysis is conversion of low
energy density substrates into higher density liquid (bio-oil) and solid
(biochar) fractions. A low-density volatile (syngas) fraction is also
produced. Pyrolysis has been utilized for millennia to produce charcoal
and coal. More recently, pyrolysis is used to produce charcoal, activated
carbon, coke, carbon ber, and methanol, among others. The distribution of products (bio-oil, biochar and syngas) is dependent on the
type of pyrolysis, reaction conditions and feedstock. Pyrolysis is classied into four categories: slow, fast, ash, and gasication. Of these,
fast and ash pyrolysis maximizes bio-oil production, slow pyrolysis
augments the yield of biochar and gasication maximizes syngas production. With regard to production of liquid transportation fuels, fast
or ash pyrolysis is employed to produce bio-oil [1114]. The properties
and composition of bio-oil such as high moisture and heteroatom content,
presence of oxygenates such as organic acids, and broad distillation curve
prevent its direct use as a transportation fuel; thus upgrading such as
hydroprocessing and distillation is necessary [1416].
Fast or ash pyrolysis has been reported on biological materials such
as wood [13], triglycerides [17], grasses [18], shrubs [19], corn cobs and
stover [20], alfalfa [21], oilseed presscakes [22], and pig compost [23],
among others. Examples of fast pyrolysis on non-biological feedstocks include scrap tires [24,25], sewage sludge [25], general municipal solid
waste [26], waste electrical and electronic equipment [27], and various
plastics [25,2836]. The plastics include polystyrene [3032], poly(vinyl
chloride) [30,31], polypropylene [3134], PE terephthalate [32], acrylonitrilebutadienestyrene [32], and PE [3032,35,36]. In some cases plastics
were co-pyrolyzed with other materials such as waste motor oil [32].
With regard to fast pyrolysis of PE, pyrolysis of LDPE [30], HDPE [35,36]
and various mixtures [31,32] was reported. In all PE studies, the properties of the resulting bio-oils were not reported, nor were the upgrading
to fuel-grade hydrocarbons and subsequent fuel property determination.
The objective of our study was the production, characterization and
evaluation of alternative diesel fuel from pyrolysis of HDPE waste grocery bags. Comparison of our pyrolyzed polyethylene hydrocarbons
(PPEH) with conventional petroleum-derived ultra-low sulfur
(b 15 ppm S) diesel (ULSD) fuel was a further objective, along with
a comparison to petrodiesel standards such as ASTM D975 and EN
590 (Table 1). Blends of PPEH with ULSD and biodiesel were prepared and the resultant fuel properties measured. It is anticipated
that these results will further understanding of the applicability

and limitations of HDPE as a feedstock for the production of alternative diesel fuel.
2. Materials and methods
2.1. Materials
Plastic HDPE grocery bags were collected from local retailers and
represent the typical ones used in grocery stores. Summer grade ULSD
was donated by a major petrochemical company. With the exception
of conductivity and corrosion inhibitor additives, ULSD contained no
performance-enhancing additives. Soybean oil methyl esters (SME)
were donated by a BQ-9000 certied commercial producer. All other
chemicals were obtained from Sigma-Aldrich Corp (St. Louis, MO). All
materials were used as received.
2.2. Pyrolysis of HDPE to produce plastic crude oil
Thermochemical conversion of plastic grocery bags (HDPE) to oils
were conducted using a pyrolysis batch reactor in triplicate. Pyrolysis
was performed in a Be-h desktop plastic to oil system (E-N-Ergy, LLC,
Mercer Island, WA) containing a 2 L reactor and oil collection system
using approximately 500 g of plastic grocery bags each time. The pyrolysis reactor has two heating zones (upper and lower); the upper and

Product yield from pyrolysis of plastic grocery bags

Gases
9%

Solid residue
17%

Plastic
crude oil
74%

Fig. 1. Product yield from pyrolysis of plastic grocery bags.

B.K. Sharma et al. / Fuel Processing Technology 122 (2014) 7990

Fraction 4 (>340C)

Table 3
Elemental analysis of waste plastic grocery bags and plastic oil distillates. (The numbers
shown are average of two measurements, while oxygen is determined by difference).

Fraction 3 (290-340C)

H, %

N, %

O, %

Cal. HHVa, MJ/kg

Waste plastic grocery bags

Waste GB
83.9

14.9

0.50

0.74

49.42

PCO5 fractions
MG
PPEH-L
PPEH-H
VGO

84.6
85.0
85.3
85.3

14.4
14.5
14.8
15.1

0.34
0.40
0.31
0.45

0.63
0.11
0.00
0.00

49.01
49.33
49.88
50.27

PCO4 fractions
MG
PPEH-L
PPEH-H
VGO

84.2
84.2
85.7
84.8

14.9
14.7
15.0
14.9

0.48
0.37
0.37
0.21

0.43
0.73
0.00
0.08

49.58
49.31
50.38
49.87

Samples

Fraction 2 (190-290C)
Fraction 1 (<190C)

0%

81

10%

20%

30%

40%

50%

Average yield, %
Fig. 2. Distillate fractions yield (%) on distillation.

lower temperatures were set to 420 and 440 C, respectively. Once the
reactor reached the set temperatures, a reaction time of 2 h was
employed from that point on. Vapors produced as a result of pyrolysis
were condensed over water as plastic crude oil (PCO). The upper oil
layer was separated and weighed. The reactor lid was opened once
the temperature was below 50 C to remove the remaining residual
solid material and weighed separately. The mass balance yields were
calculated as the ratio of the corresponding product phase (liquid and
solid) obtained in 12 batch experiments to the initial feedstock mass.
Lastly, the gas-phase yields were calculated based on the resulting
mass difference.

2.3. Distillation of plastic crude oil to yield diesel-range hydrocarbons

Distillation of PCO was performed in a Be-h desktop plastic to oil
system. A known amount of PCO (1 L) was added to the Be-h reactor
vessel. The oil collection tank was cleaned by removing the water and
dried before starting distillation. For collecting the gasoline equivalent
fraction (b 190 C), the upper and lower temperatures were set to 175
and 190 C, respectively. Once the liquid stopped dripping into the
collection vessel, the gasoline equivalent fraction was removed, ltered,
and weighed to provide yield. The upper zone temperature was then
raised to 275 C and lower zone to 290 C to collect a #1 diesel
equivalent fraction (190290 C). The # 2 diesel equivalent fraction
(290340 C) was then collected by setting the upper zone temperature
to 330 C and lower zone to 340 C. The material remaining in the reactor vessel was an atmospheric residue equivalent fraction (N 340 C),
which was removed using a siphon pump once the reactor temperature
was below 50 C. All fractions except the atmospheric residue equivalent (N 340 C) were ltered through Whatman lter paper #4 to
remove residual solid particles.

2.4. Chemical characterization of plastic oil fractions

Elemental analysis of HDPE plastic grocery bags and PCO fractions
was conducted at the University of Illinois Microanalysis Laboratory
(Urbana, IL). Samples were processed for total CHN (carbon/hydrogen/nitrogen) using an Exeter Analytical (Chelmsford, MA) CE-440
Elemental Analyzer. Oxygen was calculated by mass balance closure.

C, %

PCO1-3 fraction
PPEH-L
85.0
a

15.0
0.50
0.00
50.08



Calculated using Dulong's formula [37] HHV 0:3383C 1:422 H O8 .

2.4.1. Gas chromatographymass spectroscopy (GCMS)

Samples were analyzed for composition utilizing an Agilent (Palo
Alto, CA) model 7890 GC equipped with a model 7683 auto-injector
and a model 5975 MSD in electron impact (EI) mode. An Agilent DB35MS column (30 m 0.320 mm; 0.25 m lm thickness) was
used with a helium ow rate of 0.509 mL/min. The temperature program began with a hold at 30 C for 10 min followed by an increase at
1 C/min to 195 C, then 35 C/min to 330 C, which was held for
1 min. The injector and column transfer line heater were both set to
340 C. The detector inlet and MS quadropole temperatures were 220
and 150 C, respectively. The injection volume was 1 L with a split
ratio of 50:1. Samples (5 mg) were dissolved in heptane (1 mL). A
second set of samples was dissolved in octadecene so that compounds
of similar or shorter retention time to heptane could also be identied
and quantied. Identity of chromatographic peaks was established
from MS data, which was matched to the Agilent spectral library. The
molecular ion was observed in all cases, thus providing further corroboration of peak identity.
2.4.2. Simulated distillation by GCFID
The boiling point distribution of PCO fractions was obtained
by performing simulated distillations according to ASTM 7169.
The analysis was performed on 1% (w/w) sample solutions in
dichloromethane using an HP 5890 Series II FID gas chromatograph
equipped with a temperature programmed vaporizer injector, HP
7673 autosampler, and a Durabond DB-HT-SimDis column by Agilent
J&W Scientic (5 m 0.53 mm id, 0.15 m lm) as described by Vardon
et al. [3739].
2.4.3. Size exclusion chromatography (SEC) analysis
Molecular weight (MW) distributions were determined by SEC as
reported by Vardon et al. [3739] on a Waters (Milford, MA) Styragel
HR1 SEC column (7.8 mm 300 mm), Waters 2414 RI detector, and

Table 2
Distillate fraction yields (wt.%) of plastic crude oils (PCO) using simulated distillation (HTGCFID).
Temperature cut (C)

PCO1

PCO2

PCO3

PCO4

PCO5

Average

SD

CV

b200
200300
300400
400500
b190
190290
290340
340538

23
42
34
2
18
41
24
16

22
41
35
2
18
40
25
17

25
42
31
2
20
42
23
15

25
42
31
2
20
42
23
16

26
42
30
2
21
42
22
15

24.2
41.8
32.2
2.0
19.4
41.4
23.4
15.8

1.6
0.4
2.2
0.0
1.3
0.9
1.1
0.8

6.8
1.1
6.7
0.0
6.9
2.2
4.9
5.3

MG
PPEH-L
PPEH-H
VGO

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B.K. Sharma et al. / Fuel Processing Technology 122 (2014) 7990

Table 4
Molecular weight data on various distillates and blends using SEC.
PCO fractions

Mw

PDI

MW at peak end

PCO5 fractions
PPEH-L
PPEH-H
VGO

121
196
372

1.47
1.33
1.34

340
489
1027

PCO1-2 fractions
PPEH-L
PPEH-H
VGO

135
207
325

1.65
1.42
1.33

382
558
802

PCO1-3 fractions
PPEH-L
PPEH-H

137
212

1.61
1.38

382
627

Summer grade ULSD and blends

SG-ULSD
131
10% PPEH-H
140
20% PPEH-H
152
30% PPEH-H
160
40% PPEH-H
167
50% PPEH-H
176

2.08
2.06
1.97
1.92
1.87
1.78

299
382
382
382
382
489

THF as mobile phase (1.0 mL/min). The resulting chromatographic data

was processed using Matlab (Natick, MA) software to provide the
weight-average MW (Mw) and polydispersity index (PDI).
2.4.4. NMR and FT-IR spectroscopy
Chemical functionality information was obtained by analyzing the
fractions using Fourier-Transform infrared (FT-IR) and nuclear magnetic
resonance (NMR) spectroscopies.
1
H and 13C NMR data were collected using a Bruker Avance-500
spectrometer (Billerica, MA) running Topspin 1.4 pl8 software operating at 500 MHz (125 MHz for 13C NMR) using a 5-mm BBO probe.
Samples were dissolved in CDCl3 (Cambridge Isotope Laboratories,
Andover, MA) and all spectra were acquired at 26.9 C. Chemical shifts
() are reported as parts per million (ppm) from tetramethylsilane
based on the lock solvent.
FT-IR spectra were obtained on a Thermo-Nicolet Nexus 470 FT-IR
spectrometer (Madison, WI) with a Smart ARK accessory containing a
45 ZeSe trough in a scanning range of 6504000 cm1 for 64 scans at
a spectral resolution of 4 cm1.
2.5. Fuel properties
Properties were measured (n = 3) following AOCS, ASTM, and CEN
standard test methods using instrumentation described previously
[4042] and reported in Table 1: acid value (AV, mg KOH/g), AOCS Cd
3d-63; cloud point (CP, C), ASTM D5773; cold lter plugging point
(CFPP, C), ASTM D6371; density (g/cm3), ASTM D4052; ash point
(FP, C), ASTM D93; gross heat of combustion (higher heating value,
HHV, MJ/kg), ASTM D4809; induction period (IP, h), EN 15751; moisture content (ppm), ASTM D6304; kinematic viscosity (KV, mm2/s),
ASTM D445; lubricity (m), ASTM D6079; pour point (PP, C), ASTM
D5949; specic gravity (SG), ASTM D4052; and sulfur (S, ppm), ASTM
D5453. For a greater degree of precision, PP was measured with a resolution of 1 C instead of the specied 3 C increment. Derived cetane
number (DCN) was determined (n = 32) by Southwest Research Institute (San Antonio, TX) following ASTM D6890. Oxidation onset temperature (OT, C) was measured by pressurized differential scanning
calorimetry (PDSC) following the procedure outlined in [43]. Surface
tension (mN/m) was measured as described by Doll et al. [44].
2.6. Preparation of PPEHpetrodiesel blends
Blends were prepared at room temperature (2224 C) by pipetting
precisely measured volumes followed by agitation of the contents to

ensure homogeneity. Properties of PPEH were measured at the 10, 20,

30, 40, and 50 volume percent (vol.%) levels in ULSD. These samples
were thus labeled as P10, P20, P30, P40 and P50 as analogous to the
more commonly encountered BXX notation utilized when describing
blends of biodiesel with petrodiesel.
3. Results and discussion
3.1. Preparation and chemical composition of pyrolyzed plastics
The pyrolysis temperature range of 420440 C was chosen based
on previous studies [34]. These temperatures resulted in decomposition
reactions of HDPE to provide hydrocarbons of different chain lengths.
Pyrolysis of waste plastic grocery bags at temperatures of 420440 C
provided 74% yield of liquid product referred to as PCO, as shown in
Fig. 1. Although not determined in the present paper, literature data
suggested gaseous product obtained from pyrolysis of PE consisted
primarily of ethane and ethene (C2, 52%) and C4 (32%) compounds
[34]. The higher solid residue yield (17%) is likely due to the inorganic
content and/or char content and/or unconverted HDPE. As the pyrolysis
of PE has higher activation energy (280320 kJ/mol) compared to polypropylene (190220 kJ/mol), therefore, increasing the pyrolysis temperature to certain extent could result in increased amounts of the
liquid fraction [34]. Also, this residue may have been the fraction boiling
above 420 C (analogous to the higher boiling vacuum gas oil fraction,
VGO from petroleum distillation). Further thermal cracking of this product could have been achieved by increasing pyrolysis temperature and/
or time, which we speculate would have resulted in higher yields of the
desired PCO fraction. This residue along with the VGO fraction from PCO
have potential to be used as lubricant basestocks, which upon further
rening such as dewaxing/wax isomerization may yield API Group II/
III lubricant base oils.
The PCO thus obtained after pyrolysis of waste plastic grocery bags
was distilled into four fractions (b 190; 190290; 290340; and 340+
C equivalent of motor gasoline (MG), diesel#1 (PPEH-L), diesel #2
(PPEH-H) and VGO respectively. The product yields are represented in
Fig. 2. Similar results were obtained from SimDist analysis of PCOs
with maximum coefcient of variation ranging from 0 to 7% (Table 2).
In the absence of a catalyst, the major product is PPEH-L (41%). The
product distribution can be changed with the use of zeolite catalysts
such as ZSM-5, which will increase conversion to more low boiling
products, such as MG and PPEH-L [34].
Elemental analysis of waste plastic grocery bags and PCO fractions
revealed less than 0.5% nitrogen content and less than 0.7% oxygen content (Table 3). As expected, waste plastic grocery bags have an empirical
formula of CH2.1N0.005O0.007 quite similar to that of polyethylene (CH2).
Higher carbon and hydrogen content and lower oxygen and nitrogen
content resulted in a higher calculated HHV [3739] of 4950 MJ/kg
for most of the fractions, making these high energy liquid fuels
(Table 3). The calculated values were slightly higher than the actual
determinations (Table 1).
Analysis by SEC was employed to determine the MW distribution of
constituents in PPEH-L, PPEH-H and ULSD. The weight-average MW
(Mw), PDI, and MW at peak end were determined from a retention
time calibration curve and signal intensities from SEC data of the PCO
fractions. Corresponding to the lower temperature range collected during distillation for PPEH-L (190290 C) relative to PPEH-H
(290340 C), PPEH-L displayed a lower MW than PPEH-H. Such results
indicated that, on average, the MW of constituents in PPEH-L was lower
than that of PPEH-H (Table 4). Comparison to the MW obtained for
ULSD (Mw of 131 with max MW of 299 g/mol) revealed greater similarity to PPEH-L than PPEH-H. For most of the PCO fractions polydispersity
index (PDI) ranged between 1.33 and 1.65, thus indicating a narrow distribution of MWs for these fractions compared to the ULSD exhibiting a
higher PDI (2.08). This resulted in higher PDI of PPEHULSD blends
compared to PCO fraction (PPEH-H). As expected, upon increasing

B.K. Sharma et al. / Fuel Processing Technology 122 (2014) 7990

83

Fig. 3. Simulated distillation of a plastic crude and its four fractions.

amounts of PPEH-H in ULSD, the Mw increased due to the higher Mw of

PPEH-H (212) relative to ULSD (131).
The boiling point distribution of PCO fractions was obtained using
high temperature GCFID. Table 2 shows that the method developed
for boiling point distribution was repeatable with a CV of less than 7%
for distribution of various fractions in PCO and was similar to actual distillation data. All PCOs contained a large percentage of fraction 2 (PPEHL) followed by PPEH-H and MG. Around 98% of the PCO was distilled
under 400 C, which is a good range for producing various fuels such
as naphtha, gasoline, aviation fuel, diesel, and fuel oil. The boiling
point distribution of PCO and its four fractions is shown in Fig. 3. As
boiling point and MW distribution of PCO were similar to petroleum
fractions and contained negligible heteroatom content, therefore, we
speculate that these PCOs will be compatible with petroleum crude oil
for rening in a conventional renery. The compatibility is further

depicted in 1050% blends of PPEH in ULSD as shown in Fig. 4. As the

PPEH content increased in ULSD, the boiling point distribution shifted
towards the higher boiling range, although overall the mixture
remained within the boiling range of diesel fuel.
Compositional analysis by NMR spectroscopy revealed the presence
of aromatic, olenic and parafnic protons in PPEH-L and PPEH-H. As
seen in Table 5, aromatics comprised 1.0 and 0.6% of the overall proton
content of PPEH-L and PPEH-H, respectively. Unsaturated protons
(aliphatic olens) constituted 5.4% and 2.6% of PPEH-L and PPEH-H, respectively. The remainder of the content of PPEH-L (94.0%) and PPEH-H
(96.8%) was composed of aliphatic saturated hydrocarbons. No oxygenated species such as carboxylic acids, aldehydes, ketones, ethers, or alcohols were detected by either 1H or 13C NMR spectroscopies. Results
obtained from FT-IR analysis, Fig. 5, conrmed those collected by
NMR. The FT-IR spectrum was dominated mainly by aliphatic peaks,

84

B.K. Sharma et al. / Fuel Processing Technology 122 (2014) 7990

Fig. 4. Simulated distillation of SG-ULSD and its blends with PPEH.

consistent with high energy density, and included strong CH stretching

(30002800 cm1) and CH bending (1465 cm1, 1375 cm1) signals.
The principal constituents in PPEH-L and PPEH-H were quantied by
GCMS, as depicted by a representative chromatogram (Fig. 6). In
agreement with the NMR results, both samples were comprised of a

series of saturated and unsaturated hydrocarbons. The results, presented in Table 6, demonstrated that both fuels were composed of a mixture
of hydrocarbons. However, PPEH-H contained heavier constituents, in
agreement with SEC data and depicted in Fig. 6. GCMS results further
revealed that PPEH-L contained 43.6% (peak area) of compounds

B.K. Sharma et al. / Fuel Processing Technology 122 (2014) 7990

Table 5
Relative percentages of aromatic, olenic and parafnic protons in PPEH-L, PPEH-H and
ULSD as determined by 1H NMR spectroscopy.a,b

PPEH-L
PPEH-H
ULSD

Aromatics (%)

Olens (%)

Parafns (%)

1.0
0.6
5.2

5.4
2.6
0

94.0
96.8
94.8

Parafns = aliphatic alkanes; olens = aliphatic alkenes.

Percentages determined using integration values obtained from 1H NMR spectra of
signals corresponding to chemical shifts indicative of the functionalities indicated
(aromatics: 6.78.0 ppm; olens: 4.56.0 ppm; saturates: 0.53.0 ppm).
b

containing one or more double bonds (olens), while PPEH-H

contained 28.2% of such olen peaks. It was demonstrated earlier by
others as well that the total olen content of light oil and gasoline was
around 47% [34]. In PPEH-L, all of the components contained less than
20 carbons, and molecules as small as octane were observed, which
was similar to petroleum diesel typically containing between 8 and 21
carbon atoms per molecule. Isomers in the range of C-11 to C-13 were
the most common in PPEH-L. The PPEH-H sample contained less of
these smaller chains, with the highest concentration in the range of C16 to C-18 isomers. Alkanes of up to 23 carbons were observed in this
fuel. (Fig. 7.)

3.2. Properties of PPEH and comparison to ULSD

To demonstrate that PCOs obtained by pyrolysis have utilization in
existing reneries, diesel like fuels (PPEH-L and PPEH-H) obtained
from PCO were compared with ULSD to demonstrate their applicability
and limitations.
Depicted in Table 1 are fuel properties of PPEH-L, PPEH-H, a 1:1
blend of PPEH-L with PPEH-H, and ULSD along with a comparison to
the petrodiesel standards ASTM D975 and EN 590. PPEH-L exhibited
exceptional CP, CFPP and PP values of 30.1, 31.0 and 37.3 C,
respectively. Such properties represented a signicant enhancement
over ULSD, which provided CP, CFPP and PP values of 17.5, 16.0
and 20.3 C, respectively. However, PPEH-H, with its greater content
of higher-melting longer-chain parafnic constituents relative to
PPEH-L and ULSD (Table 6), provided CP (4.7 C), CFPP (3.7 C) and
PP (4.0 C). The 1:1 PPEH-L/H blend, representative of summer grade
ULSD, yielded cold ow properties (CP 5.9 C, CFPP 6.0 C, and PP
8.3 C) intermediate to those of the neat materials, but not as favorable as ULSD.

3000

2500

2000

1500

cm-1
Fig. 5. The FT-IR spectra of PPEH-H (top), PPEH-L (middle), compared to ULSD (bottom),
showing pure hydrocarbon content of all three fuels.

85

EN 590 prescribes a minimum oxidative stability (IP, 110 C) of

20 h whereas ASTM D975 contains no such specication. Both
PPEH-L (3.9 h) and PPEH-H (12.9 h) did not meet the threshold prescribed in EN 590. The 1:1 PPEH-L/H blend also was below the minimum limit (7.7 h). The IP of ULSD (N 24 h) conformed to the limit
specied in EN 590. The presence of unsaturated constituents
(Table 5) was speculated as the reason for the reduced stabilities of
PPEH-L and PPEH-H versus ULSD. The lower content of olenic compounds in PPEH-H (28.2%) was postulated as the cause for its enhanced stability relative to PPEH-L (43.6%). Employment of
antioxidants improved the stabilities of PPEH-L, PPEH-H and their
1:1 mixture. Specically, 1000 ppm BHT yielded IPs N 24 h for
PPEH-H and the 1:1 mixture, thus exceeding the threshold specied
in EN 590. However, PPEH-L treated with BHT was below the minimum limit (14.4 h), which indicated that a hydrogenation step may
be required before its use as a blend component in ULSD.
Both the American and European petrodiesel standards contain
specications for KV at 40 C with ASTM D975, prescribing a range of
1.94.1 mm2/s and EN 590 specifying a range of 2.04.5 mm2/s. The
KV of PPEH-L (1.20 mm2/s) was below the minimum limits due to its
high content of shorter-chain, lower MW constituents. Both PPEH-H
(2.96 mm2/s) and ULSD (2.28 mm2/s) exhibited KVs within the ranges
specied in the standards. The KV of the 1:1 PPEH-L/H mixture
(2.08 mm2/s) was in between the values obtained for the neat materials
and conformed to the limits specied in ASTM D975 and EN 590.
ASTM D975 and EN 590 specify minimum limits for CN of 40 and 51,
respectively. PPEH-L (54.6) and PPEH-H (73.4) exhibited DCNs meeting
the limits specied in the standards and are higher than that obtained
for ULSD (47.4). An earlier study reported cetane numbers in the
range of 6269 for light oils prepared from pyrolysis of HDPE [34]. The
higher DCN of PPEH-H versus PPEH-L was attributed to its higher
content of longer-chain parafns, as longer chains result in higher
DCNs [45]. A DCN of 66.3 was observed for the 1:1 PPEH-L/H mixture,
which was in between the neat materials and above the limits specied
in ASTM D975 and EN 590.
The minimum limits prescribed for FP in ASTM D975 and EN 590 are
52 and 55 C, respectively. Due to its comparatively high content of
shorter-chain, low MW constituents, PPEH-L exhibited a FP (b30 C)
signicantly below the minimum limits specied in the petrodiesel
standards, and also considerably lower than the values obtained for
PPEH-H (81.5 C) and ULSD (65.0 C). Accordingly, the 1:1 PPEH-L/H
mixture exhibited a FP of 90.3 C and was within the limits prescribed
in ASTM D975 and EN 590.
Maximum wear scars of 520 and 460 m are specied as upper limits
for lubricity (60 C) in ASTM D975 and EN 590. All of the PPEH samples
provided wear scars signicantly below the thresholds listed in the
petrodiesel standards. The longer wear scar noted for PPEH-L
(293 m) versus PPEH-H (198 m) was speculated to be due to the
higher content of longer-chain constituents in PPEH-H, as increasing
chain length results in lower wear and consequently shorter wear scar
lengths [46]. The wear scar obtained for ULSD (581 m) was above the
upper limits prescribed in the standards and signicantly longer than
observed for the PPEH samples.
Sulfur, which poisons vehicle emissions control devices and contributes to environmental pollution, is limited to maximum levels of 15 and
10 ppm in ASTM D975 and EN 590. The concentrations of sulfur in all
samples, including ULSD, were below 10 ppm. Similarly, the content
of moisture in all samples was below the maximum limit of 200 ppm
prescribed in EN 590. ASTM D975 does not contain a moisture
specication.
ASTM D975 does not contain limits on density, but EN 590 species a
density of 820845 kg/m3 at 15 C. Neither PPEH-L (776 kg/m3) nor
PPEH-H (802 kg/m3) provided densities meeting the range specied
in EN 590. Accordingly, the density of the 1:1 PPEH-L/H blend
(791 kg/m3) was below the minimum limit. ULSD conformed to EN
590 with a density of 849 kg/m3. The lower densities of the PPEH

86

B.K. Sharma et al. / Fuel Processing Technology 122 (2014) 7990

Fig. 6. The GCMS chromatogram of PPEH-H showing the separation of the alkane and alkene components of the mixture over the rst 170 min of run-time.

samples versus ULSD may be attributed to the greater percentage of aromatics in ULSD. Aromatics exhibit higher densities than linear,
branched and cyclic hydrocarbons more commonly encountered in
the PPEH samples [47]. The higher density of PPEH-H versus PPEH-L
may be attributed to the higher content of longer-chain constituents

Table 6
Principal constituents (area %) identied by GC-MS in PPEH-L and PPEH-H.

C8-alkane
C8-alkene
C9-alkane
C9-alkene
C10-alkane
C10-alkene
C11-alkane
C11-alkene
C12-alkane
C12-alkene
C13-alkane
C13-alkene
C14-alkane
C14-alkene
C15-alkane
C15-alkene
C16-alkane
C16-alkene
C17-alkane
C17-alkene
C18-alkane
C18-alkene
C19-alkane
C19-alkene
C20-alkane
C20-alkene
C21-alkane
C21-alkene
C22-alkane
C23-alkane
a

N/D = not detected.

PPEH-L

PPEH-H

2.5
2.6
4.8
4.0
6.3
5.9
7.7
7.1
8.2
6.9
7.9
6.5
6.9
5.0
5.4
3.2
3.5
1.7
2.0
0.6
1.0
0.1
0.3
N/D
N/D
N/D
N/D
N/D
N/D
N/D

N/Da
N/D
0.04
0.04
0.1
0.1
0.3
0.3
1.2
1.0
3.2
2.3
6.2
4.1
9.5
5.4
11.3
5.9
11.6
4.6
10.4
2.5
8.0
1.4
5.5
0.5
3.0
0.1
1.5
0.1

in PPEH-H, as these tend to have higher densities than shorter-chain hydrocarbons. Also measured was SG, which is not specied in either
ASTM D975 or EN 590. As was the case with density and for essentially
the same reasons, the SGs of PPEH-L (0.777) and PPEH-H (0.803) were
lower than observed for ULSD (0.841). Correspondingly, the SG of the
1:1 PPEH-L/H mixture (0.792) was in between the neat materials and
lower than ULSD.
Although ST is not specied in either ASTM D975 or EN 590, it
nevertheless inuences fuel atomization in combustion chambers of
diesel engines [48]. The STs of PPEH-L (22.5 mN/m) and PPEH-H (24.7
(mN/m) at 40 C were below ULSD (25.1 mN/m). It is speculated that
the higher content of longer-chain constituents in PPEH-H was responsible for its higher ST versus PPEH-L, as a positive correlation between
chain length and ST was established previously [44]. Consequently,
the ST of the 1:1 PPEH-L/H blend (23.6 mN/m) was in between the
values obtained for the neat materials and lower than ULSD.
The HHVs of PPEH-L (45.86 MJ/kg) and PPEH-H (46.16 MJ/kg) along
with the 1:1 blend (46.04 MJ/kg) were higher than ULSD (45.15 MJ/kg).
It was no surprise that the HHV of PPEH-H was greater than PPEH-L, as
larger hydrocarbons generally contain more energy content. The higher
HHVs of the PPEH samples relative to ULSD was attributed to the higher
content of aromatics in ULSD, as aromatics contain less energy than saturated constituents found in higher abundance in PPEH. Energy content
is not specied in the petrodiesel standards.
The discussion above demonstrated that PPEH-L, PPEH-H, and PPEHL/H had good properties for further fuel-like utilization similar to petroleum diesel.
3.3. Properties of PPEH blended with ULSD
Depicted in Tables 7 and 8 are fuel properties of PPEH-L (Table 7)
and PPEH-H (Table 8) blended with ULSD. For each sample, blends of
10 (P10), 20 (P20), 30 (P30), 40 (P40) and 50 (P50) vol.% in ULSD
were investigated. With regard to cold ow properties, as the percentage of PPEH-L increased in blends with ULSD, values for CP, CFPP and
PP became progressively lower due to the superior low temperature

B.K. Sharma et al. / Fuel Processing Technology 122 (2014) 7990

PPEH-L
PPEH-H

Chromatogram area (%)

15

10

0
5

10

15

20

25

Carbon number
Fig. 7. The composition of PPEH-H and PPEH-L vs. carbon number.

performance of PPEH-L relative to ULSD. In the case of PPEH-H, the opposite trend was elucidated in which cold ow properties (CP and PP)
deteriorated as the concentration of PPEH-H in ULSD increased. CFPP
of PPEH-H was not measured due to insufcient sample. Similarly, oxidative stability decreased as the percentage of PPEH increased in blends
with ULSD. Comparison to the IP specication in EN 590 revealed that
only the P1030 blends of PPEH-H were above the minimum specication of 20 h. Results obtained from measurement of OT corroborated
those obtained for IP: deterioration of stability as the concentration of
PPEH increased in ULSD as indicated by progressively lower OTs.
Because the order of KV of neat materials was PPEH-L (lowest)
b ULSD b PPEH-H (highest), opposite trends were noticed when
PPEH-L and PPEH-H were blended with ULSD. Specically, lower KVs
were noted as the concentration of PPEH-L increased in blends with
ULSD whereas higher KVs were observed with progressively higher
concentrations of PPEH-H. Comparison to fuel standards listed in
Table 1 revealed that all PPEH-H blends along with the P10 PPEH-L/
ULSD were within the limits prescribed in the petrodiesel standards.
However, the P30P50 PPEH-L/ULSD samples did not conform to the
petrodiesel standards. The P20 PPEH-L/ULSD sample was satisfactory
when compared against ASTM D975 but not EN 590.
As the concentration of PPEH-L and PPEH-H in ULSD increased,
progressively higher DCNs were obtained. All blends met the minimum
limit of 40 prescribed in ASTM D975, but only the P20P50 blends of
PPEH-H and the P50 blend of PPEH-L satised the more stringent

87

threshold of 51 specied in EN 590. The low DCN of ULSD relative to

the PPEH samples was speculated as the reason for the low DCNs of
low-level blends of PPEH-L/H in ULSD.
Opposite trends were noted with regard to FP of PPEH-L and PPEH-H
blends in ULSD. Specically, FP decreased as the percentage of PPEH-L
increased in blends with ULSD whereas higher FPs were noted as the
content of PPEH-H increased in blends. All of the PPEH-H blends were
within the limits prescribed in ASTM D975 and EN 590 whereas none
of the PPEH-L blends met the limits set forth EN 590. The P10 PPEH-L/
ULSD blend was above the minimum FP specied in ASTM D975. The
lower FPs of the PPEH-L blends relative to the PPEH-H was postulated
to be due to the signicantly lower FP of neat PPEH-L versus neat
PPEH-H.
Progressively shorter wear scars were observed as the concentration
of PPEH increased due to the enhanced lubricities of PPEH-L and PPEHH relative to ULSD. The effect was more pronounced in the case of PPEHH, as it exhibited better lubricity than PPEH-L. With the exception of the
P10 PPEH-L blend, the lubricities of all blends were below the maximum
limit specied in ASTM D975. However, only the P20P50 PPEH-H and
P40P50 PPEH-L blends were below the more stringent limit specied
in EN 590.
Density as well as SG decreased as the percentage of PPEH increased
in blends with ULSD. The effect was greater for PPEH-L blends, as the
density and SG of PPEH-L were lower than those of PPEH-H, which in
turn were lower than the corresponding values for ULSD. All blends
with the exception of the P40 and P50 blends with PPEH-L provided
densities that fell within the range specied in EN 590.
All PPEH-L and PPEH-H blend samples were below the maximum
allowable limits listed in the petrodiesel standards for sulfur content.
Furthermore, all blend samples contained less than 80 ppm moisture,
thus conforming to the upper limit of 200 ppm set forth in EN 590.
Lastly, energy content of the blend samples did not vary signicantly
with concentration of ULSD. For both PPEH-L and PPEH-H blends, HHV
increased slightly with increasing percentage of PPEH due to the higher
energy contents of PPEH-L and PPEH-H versus ULSD.

3.4. Inuence of blending biodiesel with PPEH

Due to the emergence of biodiesel (fatty acid methyl esters prepared
from lipids) as a signicant source of alternative diesel fuel and its
industrial production as evidenced by separate ASTM (D6751) and EN
(14214) standards governing its composition and properties, blends of
biodiesel with PPEH were investigated herein [49,50]. Because soybean
oil is the principal feedstock for production of biodiesel in the U.S., thus
resulting in SME, it was of interest to the current study [49]. Shown in
Table 9 are B2 and B5 blends of SME in PPEH-L, PPEH-H and ULSD

Table 7
Fuel properties of pyrolyzed polyethylene hydrocarbons (PPEH-L) blended with ULSD.a
Units
Low temperature
CP
PP
CFPP
Oxidative stability:
IP, 110 C
OT
KV, 40 C
DCN
Flash point
Wear scar, 60 C
Sulfur
SG, 15 C
Density, 15 C
Moisture
HHV
a

P10

P20

P30

P40

P50

15.9 (0.1)
25.3 (0.6)
17.7 (0.6)

16.8 (0.2)
27.7 (0.6)
19.7 (0.6)

17.9 (0.1)
29.3 (0.6)
21.0 (0)

19.3 (0.1)
30.7 (0.6)
24.7 (0.6)

20.7 (0.1)
31.3 (0.6)
26.0 (0)

16.5 (1.6)
194.9 (0.1)
2.11 (0)
48.4 (0.9)
54.0 (0.7)
538 (5)
8
0.835 (0)
834 (1)
55 (1)
45.22 (0.10)

10.0 (0.2)
190.8 (0.8)
1.96 (0)
48.9 (0.9)
48.5 (0.7)
512 (4)
8
0.829 (0.001)
828 (0)
56 (2)
45.20 (0.09)

7.6 (0.1)
187.2 (0.9)
1.83 (0)
49.8 (1.0)
38.0 (0.7)
463 (7)
7
0.822 (0)
822 (1)
63 (1)
45.18 (0.12)

7.1 (0.1)
185.6 (0.8)
1.71 (0)
50.4 (0.9)
34.5 (0.7)
446 (2)
6
0.816 (0.001)
815 (0)
72 (2)
45.26 (0.14)

6.3 (0.5)
183.0 (0.6)
1.60 (0)
51.4 (1.0)
32.0 (1.4)
422 (7)
5
0.809 (0)
809 (1)
79 (1)
45.56 (0.14)

h
C
mm2/s
C
m
ppm
kg/m3
ppm
MJ/kg

Values in parentheses represent standard deviations from the reported means (n = 3). For ash point, n = 1.

88

B.K. Sharma et al. / Fuel Processing Technology 122 (2014) 7990

Table 8
Fuel properties of pyrolyzed polyethylene hydrocarbons (PPEH-H) blended with ULSD.a
Units
Low temperature
CP
PP
Oxidative stability
IP, 110 C
OT
KV, 40 C
DCN
Flash point
Wear scar, 60 C
Sulfur
SG, 15 C
Density, 15 C
Moisture
HHV
a

P10

P20

P30

P40

P50

12.4 (0.1)
17.0 (0)

9.9 (0.1)
14.3 (0.6)

7.5 (0.2)
10.3 (0.6)

5.7 (0.2)
8.7 (0.6)

3.7 (0.1)
5.3 (0.6)

21.1 (1.7)
194.7 (0.1)
2.34 (0)
48.9 (0.8)
65.5 (0.7)
503 (8)
8
0.838 (0)
837 (0)
40 (1)
45.19 (0.03)

20.8 (1.1)
194.2 (0.6)
2.40 (0)
51.2 (0.9)
64.0 (2.8)
388 (18)
8
0.834 (0)
833 (0)
48 (2)
45.34 (0.07)

20.2 (0.5)
194.0 (0.2)
2.46 (0)
54.9 (1.0)
68.5 (0.7)
288 (7)
7
0.825 (0.004)
828 (1)
52 (1)
45.37 (0.16)

14.1 (0.8)
191.8 (0.7)
2.54 (0)
57.1 (1.1)
69.0 (0.7)
254 (13)
6
0.826 (0)
825 (1)
53 (1)
45.60 (0.10)

10.3 (0.1)
192.0 (0.7)
2.60 (0)
59.3 (1.0)
69.0 (1.4)
256 (10)
5
0.823 (0)
822 (1)
60 (1)
46.03 (0.09)

h
C
mm2/s
C
m
ppm
kg/m3
ppm
MJ/kg

Values in parentheses represent standard deviations from the reported means (n = 3). For ash point, n = 1.

along with neat SME (B100). Addition of SME to PPEH-H and ULSD
resulted in lower IP and OT as the percentage of SME increased. The
stability of PPEH-L was unaffected upon SME addition due to the similar
IPs of neat SME (4.6 h) and PPEH-L (3.9 h). As the concentration of SME
in PPEH-L and ULSD increased from B0 to B5, progressively higher CP
and PP values were noted. In the case of PPEH-H, the opposite trend
was noticed. The reason for this behavior was due to the order of cold
ow properties of the neat materials: PPEH-H (highest CP and PP)
N SME NN ULSD NN PPEH-L (lowest CP and PP). The higher KV of neat
SME (4.09 mm2/s) relative to PPEH-L, PPEH-H and ULSD resulted in progressively higher KVs as the blend percentage of SME increased. Due to
the excellent lubricity of SME (152 m), signicant reductions in wear
scar length were noticed as the percentage of SME increased in the
blends. Comparison to the petrodiesel standards revealed that blends
of SME with PPEH-H and ULSD were within the specications for lubricity and KV. However, the PPEH-L blends satised the lubricity limits but
did not fall within the ranges specied for KV. It was found that diesel
obtained from pyrolysis of plastic is as compatible with biodiesel as
ULSD due to quite similar hydrocarbon structures and chain length distribution of molecules.
Depicted in Table 10 is the inuence on cold ow properties of blending 5, 10 and 20% PPEH-L, PPEH-H and ULSD with SME along with a comparison to neat SME. In the case of PPEH-H, CFPP was not determined due
to lack of sample availability. Both PPEH-L and ULSD were effective at depressing cold ow properties of SME, although the inuence was linear as
opposed to additive. PPEH-H, with its inferior cold ow properties, caused
CP and PP to increase as the percentage of PPEH-H was increased in
blends with SME.
4. Conclusions
Pyrolysis of HDPE waste plastic grocery bags followed by distillation
resulted in a major liquid hydrocarbon product (PPEH-L) with average

structure consisting primarily of saturated aliphatic parafnic hydrogens (94.0%) and smaller amounts of aliphatic olenic hydrogens
(5.4%) and aromatic hydrogens (1.0%) that corresponded to the boiling
range typical of conventional petroleum diesel fuel (190290 C).
Negligible heteroatom-containing species were detected from elemental analysis. Also obtained was a heavier boiling fraction (290340 C)
equivalent of diesel#2 from distillation of the crude pyrolysis product,
PPEH-H, which also consisted of parafnic protons (96.8%), olenic protons (2.6%) and aromatic protons (0.6%). Based on the results obtained
after determination of fuel properties and comparison to petrodiesel
standards, the following conclusions were made regarding the applicability of these materials as alternative liquid transportation fuels:
1. PPEH-H is more appropriate as an alternative diesel fuel because it
exhibited higher values for FP, IP, KV, DCN, HHV, density, and lubricity than PPEH-L.
2. PPEH-H, after addition of antioxidants, met all ASTM D975 and EN
590 fuel specications with the exception of density in the case of
EN 590.
3. PPEH-L did not meet EN 590 specications for IP, KV, FP, and density
due to its higher content of lower MW constituents.
4. A 1:1 mixture of PPEH-H and PPEH-L met all ASTM D975 and EN 590
specications with the exception of density and IP in case of EN 590,
therefore PPEH-L and PPEH-H distillates can be collected together to
provide ~64% diesel equivalent fraction from pyrolysis of plastic
grocery bags.
5. P10P30 blends of PPEH-H with ULSD met all ASTM D975 specications whereas only the P20P30 blends met all EN 590 limits. P40
and P50 blends require antioxidants to meet the oxidative stability
specication listed in EN 590.
6. P10 blend of PPEH-L with ULSD met all ASTM D975 specications
except lubricity, while none of the blends of PPEH-L with ULSD met
EN 590 specications primarily due to poor DCN, IP, FP, and KV.

Table 9
Inuence of blending soybean oil methyl esters (SME) with PPEH-L and PPEH-H on fuel properties along with a comparison to blends in ULSD.a

Oxidative stability
IP, 110 C
OT
Low temperature
CP
PP
KV, 40 C
Wear scar, 60 C
a

SME

PPEH-L

Units

(B100)

B2

h
C

4.6 (0.1)
175.4 (0.5)

3.9 (0.1)
174.8 (0.9)

C
C
mm2/s
m

0.3 (0.1)
1.7 (0.6)
4.09 (0)
152 (2)

28.5 (0.1)
36.7 (0.6)
1.23 (0)
267 (2)

PPEH-H
B5

ULSD

B2

B5

3.9 (0.1)
176.5 (0.7)

6.9 (1.0)
189.9 (0.3)

6.4 (1.2)
186.5 (0.5)

19.7 (0.5)
195.6 (0.1)

18.1 (0.2)
193.7 (0.3)

26.8 (0.2)
35.7 (0.6)
1.27 (0)
201 (4)

4.6 (0.2)
4.4 (0.2)
2.98 (0)
177 (1)

4.0 (0)
3.3 (0.6)
2.99 (0)
173 (2)

16.0 (0.3)
23.0 (0)
2.31 (0)
247 (7)

14.1 (0.2)
24.3 (0.6)
2.34 (0)
231 (4)

Values in parentheses represent standard deviations from the reported means (n = 3).

B2

B5

B.K. Sharma et al. / Fuel Processing Technology 122 (2014) 7990

Table 10
Inuence of blending PPEH with SME on cold ow properties along with a comparison to
blends in ULSD.a
Sample (vol.%)

CP
(C)

CFPP
(C)

PP
(C)

SME
5% PPEH-L in SME
10% PPEH-L in SME
20% PPEH-L in SME
5% PPEH-H in SME
10% PPEH-H in SME
20% PPEH-H in SME
5% ULSD in SME
10% ULSD in SME
20% ULSD in SME

0.3 (0.1)
0.6 (0)
1.7 (0.1)
3.9 (0.2)
0.3 (0.1)
0.4 (0.1)
1.1 (0.1)
0.3 (0.2)
1.0 (0)
2.6 (0.1)

3.7 (0.6)
5.7 (0.6)
6.7 (0.6)
8.7 (0.6)
N/Db
N/Db
N/Db
4.3 (0.6)
6.7 (0.6)
8.7 (0.6)

1.7 (0.6)
3.0 (0)
4.0 (0)
6.7 (0.6)
1.0 (0)
1.0 (0)
0.0 (0)
2.3 (0.6)
3.7 (0.6)
5.0 (0)

a
Values in parentheses represent standard deviations from the reported means
(n = 3).
b
N/D = not determined.

7. Diesel obtained from pyrolysis of plastic is as compatible with biodiesel as ULSD due to similar hydrocarbon structures and chain length
distribution of molecules.
8. Biodiesel blends with PPEH-H met the specications for lubricity and
KV, while PPEH-L blends satised the lubricity limits, but not KV
limits. PPEH-L improved low temperature properties of SME biodiesel whereas PPEH-H had the opposite effect.
Based on these ndings, PPEH-H and a mixture of PPEH-H/PPEH-L
are suitable blend components for ULSD in the P10P50 blend range
so long as antioxidants are employed.
Acknowledgments
The authors acknowledge Dheeptha Murali (ISTC), Jennifer L
Deluhery (ISTC), Benetria N. Banks (USDA-ARS-NCAUR) and Erin L.
Walter (USDA-ARS-NCAUR) for excellent technical assistance. This
study was supported in part by seed funding from the Illinois Hazardous
Waste Research Fund.
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