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Experimental investigation to identify the type of waste plastic pyrolysis oil suitable for
conversion to diesel engine fuel

V.L. Mangesh, S. Padmanabhan, P. Tamizhdurai, A. Ramesh

PII: S0959-6526(19)33936-8
DOI: https://doi.org/10.1016/j.jclepro.2019.119066
Reference: JCLP 119066

To appear in: Journal of Cleaner Production

Received Date: 21 May 2019

Revised Date: 25 September 2019
Accepted Date: 26 October 2019

Please cite this article as: Mangesh VL, Padmanabhan S, Tamizhdurai P, Ramesh A, Experimental
investigation to identify the type of waste plastic pyrolysis oil suitable for conversion to diesel engine fuel,
Journal of Cleaner Production (2019), doi: https://doi.org/10.1016/j.jclepro.2019.119066.

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Graphical abstract

The experiment and analysis plan for conversion of solid waste plastics to diesel fuel.
Experimental Investigation to identify the type of waste plastic pyrolysis oil
suitable for conversion to diesel engine fuel

V.L.Mangesh*1,2, S.Padmanabhan3, P. Tamizhdurai4, A.Ramesh5

1
Sathyabama Institute of Science and Technology, Jeppiar Nagar, Chennai-600119, India.
2
Department of Marine Engineering, Coimbatore Marine College, Coimbatore-641035.
3
Department of Automobile Engineering,Vel Tech Rangarajan Dr Sagunthala R&D Institute
of Science and Technology, Avadi, Chennai-600062, India.
4
National Centre for Catalysis Research, Indian Institute of Technology (IIT), Madras,
Chennai 600 036, India
5
Department of Chemistry, Anna University, Chennai 600 025, India

*Corresponding Author

V.L.Mangesh
Email.ID: vlmangesh@gmail.com

1
Abstract

Plastics for various applications is increasing every year due to outstanding

advantages, but after use recycling and disposal have remained a challenge. In this paper,

through experiments, we compare properties of pyrolysis oil derived from after use HDPE

(High-density polyethylene), LDPE (Low-density polyethylene), PP

(Polypropylene)andstyrenefor their suitability as diesel engine fuel. This experimental study

is to identify which type of plastic is suitable for blending with diesel. The physicochemical

properties of pyrolysis oil of HDPE, LDPE, PP, and styrene were tested, tabulated and

compared with diesel. The physicochemical properties of polypropylene pyrolysis oil (PPO)

were found to be superior to the produced pyrolysis oil of HDPE, LDPE, and styrene. The

GC-MS(Gas chromatography-mass spectrometry)and FT-IR(Fourier transform-

infraredspectroscopy) were taken for pyrolysis oil of HDPE, LDPE, PP,andstyrene and

compared with diesel. PPO showed lower carbon number chain compounds compared to the

other three waste plastics. We selected PPO for diesel engine performance and emission trials

based on the results of the above tests. PPO was blended in the ratios of 5%, 10% and 15%

with diesel. Combustion analysis showed a sliincrease in cylinder pressure in comparison to

diesel values. The heat release rates (HRR) were sharply higher than diesel. Bothcylinder

pressure and HRRvalues for PPO increased as the blend ratios increased. The emission

results showed anincrease in carbon monoxide (CO), hydrocarbon (HC)and oxides of

Nitrogen (NOx)emissions. The multiple times increase in emissions is due to the presence of

unsaturated hydrocarbons and higher carbon number of saturated compounds in PPO.GC-MS

tests confirmed the presence of such compounds in PPO. To reduce the unsaturation to

negligible levels, we will take up future experiments in hydrogenating PPO with various

catalysts and test the performance and emissions in diesel engines.

Keywords: Waste plastics, Pyrolysis, Hydrogenation and Diesel Engines.

2
Nomenclature

PSW Plastic Solid Waste

FE-SEM Field-Emission Surface Electron Microscope

TPD Temperature Programmed Desorption

PP Polypropylene

LDPE Low-Density Polyethylene

HDPE High-Density Polyethylene

PPO Polypropylene Pyrolysis Oil

5 PPO 5% polypropylene pyrolysis oil + 95% diesel

10 PPO 10% polypropylene pyrolysis oil + 90% diesel

15 PPO 15% polypropylene pyrolysis oil + 85% diesel

HRR Heat Release Rate

BTE Brake Thermal Efficiency

BSFC Brake Specific Fuel Consumption

CO Carbon monoxide

HC Hydrocarbon

NOx Oxides of Nitrogen

3
1. Introduction

The application of plastics in domestic and industrial applications is increasing day by

day.The benefits of plastics are in the ease of manufacturing, low weight and lesser cost [1].

A continuous research in polymer technology is making plastics suitable for applications

which require higher strength and thermal stability [2]. Dupont products like Zytel HTN are

latest development products, which deliver excellent strength, impact and stiffness

performance, compared to not only metal but also to other glass fiber reinforced polyamides.

The disadvantage of plastics is in the disposal after a useful life. Plastics are not

biodegradable, it takes more than 400 years to degrade, only 9% are mechanically recycled,

12% incinerated, and balance fills the land and oceans [3]. In Europe, the plastic collected

post-consumer waste through the official scheme is 27.3 million tonnes for 2016, whereas

European plastic consumption was 50 million tonnes [4]. The data shows that the waste

collection of plastics has reached only about 50% of the consumption. Useful recycling has a

long way to proceed towards the 100% target. The strategies to reduce plastic pollution is

listed in the order of lesser environmental safety-reduce usage, reuse, recycling of plastic

materials and recovery of energy, with landfill as the least option [5].There have been

innovative recycling of plastics by adopting concepts such as chemically recyclable

polymers. The concept has been achieved by two types of chemical recycling, repurposing,

and depolymerization. Huang and Guan et al. reported a repurposing process of various types

of polyethylene materials into liquid fuels (diesel) and waxes under relatively mild conditions

[6].Recycling ofplastic solid waste (PSW)into building materials like tiles have been

attempted to get reduced flammable and high strength materials. Waste plastic matrix

reinforced with fly ash and a flame retardant at different loadings were molded into

composite tiles [7].The focus of our research is in the strategy of energy recovery from PSW.

The PSW to energy process conversion results in net energy savings [8]. Pyrolysis of PSW

4
produces hydrocarbon liquids. Pyrolysis is effectively achieved by thermal pyrolysis method

at 400 to 900 oC[9] or through catalytic pyrolysis method [10]. The latter provides better oil

yield at lower temperatures [11]. PSW degradation through thermal pyrolysis is normally a

low selectivity reaction, whereas degradation through catalytic pyrolysis improves the

selectivity of reaction [12]. An acidic catalyst like zeolites is found to be effective in the

conversion of PSW to pyrolysis oil [13-15]. Catalytic cracking mechanism increases the

yields of alkanes and aromatics. It also increases the reaction rate by the below-mentioned

carbonium ion mechanism of acidic catalysts. Four mechanisms describe the catalytic

mechanism. The first one is initiation, which converts an olefinic linkage into an on-chain

carbonium ion by proton addition. Subsequently, the polymer chain can be broken up by β-

scission. Second by depropagation, a process in which the long polymer chains may be

cracked through attacks by acidic sites and further breaking by β-scission to produce lower

carbon number liquid fraction. Third by isomerization, a process in which the carbonium ion

substituents may undergo rearrangement by hydrogen. Fourth is aromatization, a process in

which some carbonium ion substituents may undergo cyclization reactions [16]. Pyrolysis is

the first step of conversion of PSW to oil. The converted oil contains saturated and

unsaturated compounds, whereas diesel oil is mostly comprised of saturated bonds [17-19].

The kinetic studies by Sorumetal. [20] show that the dissociation energy of single bond C-C

is 347 KJ/mole, whereas that of double bond C=C is 611KJ/mole. The high dissociation

energy results in high HRR during combustion and hence PSW pyrolysis oil becomes

unsuitable for combustion in diesel engines. The PSW pyrolysis oil should be further treated

to convert unsaturated bonds to saturated bonds. Some of the commonly used plastics like

HDPE, LDPE, PP, and styrene were selected for our study, and they together form 65% of

the world resin demand [21]. In this experimental study, we have selected ZSM-5 as a

catalyst. ZSM-5 was synthesized and used as a catalyst for pyrolysis of all the four selected

5
waste plastics. The same catalyst and process conditions were used for the pyrolysis to enable

comparison and determine the type of plastic which produces pyrolysis oil having diesel-like

characteristics. Catalytic cracking has been attempted by using liquid-phase contact mode

instead of vapor phase contact mode. The fluid cracking method has given good oil yields for

PP in this study. The objective of this study is to select the type of plastic suitable for

conversion to diesel fuel. Four types of waste plastic selected and each converted to liquid

fuel through catalytic pyrolysis. Catalytic conversion behaviour of each type examined.

Physicochemical properties were tested to analyse and compare the fuel injection

characteristics with diesel. FT-IR studies conducted to compare the presence of functional

groups in each type ofproduced pyrolysis oil with that of diesel. GC-MS tests were utilised to

study the chemical composition of each type of produced pyrolysis oil and compare it with

diesel. The tests enabled to investigate the presence of saturated and unsaturated compounds.

The target is to choose the type of waste plastic which after conversion to pyrolysis oil can

provide an environmentally friendly diesel fuel.

2. Experimental

2.1 Synthesis of micro-mesoporous zeolite ZSM-5 catalyst

The following chemicals without any further purification have been used in the

synthesis of ZSM-5. Tetraethylorthosilicate (TEOS), 3-[(trimethoxysilyl) propyl]

octadecyldimethylammoniumchloride (ODAC, 60% methanol solution) were acquired from

Sigma Aldrich. Tetrapropylammonium bromide (TPABr) and metakaolin were acquired from

SD Chemicals. Micro-mesoporous ZSM-5 molecular sieves were synthesized hydrothermally

from a reaction gel containing 3-[(trimethoxysilyl)propyl] octadecyl dimethyl ammonium

chloride (ODAC, 60% methanol solution) and tetrapropylammonium bromide (TPABr) as a

template by following a modified synthesis of previously reported procedures[22]. The

synthesis gel was prepared as follows: solution A was prepared by adding 0.4 g of NaOH

6
pellets, followed by the addition of 1.4 g of TPABr and 0.5 g of metakaolin in 67.5 g of

distilled water under vigorous stirring at room temperature for 30 minutes until the solution

became homogeneous. Finally, a gel was obtained by adding a homogenous mixture of 4.285

g of TEOS (tetraethyl orthosilicate) and 0.595 g of ODAC with solution A under vigorous

stirring for 2h. Gels with chemical compositions containing different amounts of ODAC are

represented by the formula, 1Al2O3:2.33TPABr:2.22Na2O:11.04-11.85SiO2:0.26–

1.6ODAC:1666H2O which were prepared to obtain the different ZSM-5 samples. The

mixture was then transferred to a stainless-steel autoclave, heated in an oven at 150°C for

24h. The obtained crystallized product was washed, dried at 100°C overnight and calcined in

air at 550°C for 6h with a heating rate of 1°C per min. Ammonium exchanged commercial

ZSM-5 zeolite with a SiO2/Al2O3 ratio of 50 (SAR = 50), was obtained from Zeolyst

International and was used in XRD analysis.

2.2Characterisation of ZSM-5

FE-SEM and EDS analysis of synthesized ZSM-5 was done to study the morphology

and element distribution of the catalyst. FE-SEM and EDSwere done on MIRA 3 TESCAN

equipment. TPD analysis of synthesized ZSM-5 was done to study the acidity of the catalyst.

The acidity of the sample was characterized by adopting the temperature-programmed

desorption technique using ammonia (NH3-TPD) as probe gas. TPD results were obtained

with an instrument (Micromeritics Chemisorb 2750).

2.3 Material and methods for pyrolysis

The methodology adopted for the experimental study has been explained by using a

flow chart(Scheme 1). Four types of PSW were selected and pyrolysis of each type

conducted. Bottles, cans, and containers made from HDPE, LDPE, PP and styrene materials

were selected for the study. The selected plastics are colorless (milky white) , and colored

7
plastic were avoided to prevent dye and pigments influencing pyrolysis results. The selected

plasticswere shredded to 2mm size.

Physicochemical, GC-MS and FTIR tests were conducted for each type of produced

pyrolysis oil. Tests results favored PPO for blending with diesel. The blended fuel was trial

tested in diesel engines and results analyzed.

The catalytic conversion of the selected plastics was carried out in a semi-batch

reactor. The reactor and muffle furnace, as shown in Fig.1was fabricated at Hashtha

Scientific Instruments Pvt Ltd. The muffle furnace has a maximum operating temperature of

800°C and 1.5KW rating. The digital controller is used to control and maintain the

temperature in conjunction with Cr/A1 thermocouple. The stainless-steel reactor has a tube

length of 250mm and an internal diameter of 50mm. Vacuum inside the reactor was

maintained by a vacuum pump to enable pyrolysis to take place. 25 grams of ZSM-5 catalyst

was added to 100 grams of waste plastics (1:4 ratio). Selected 1:4 ratio for the experimental

studies as this ratio has provided maximum yield [23].

2.4 Physicochemicaltest for Pyrolyis Oil and Diesel

The pyrolysis oil of four selected waste plastics and diesel were tested

forphysicochemical properties under IS standards.

2.5 FT-IR and GC-MS Analysis

FT-IR studies were carried out using a Nicolet 6700 FT-IR spectrophotometer. GC-

MS was done in Thermo GC-Trace Ultra VER: 5.0, Thermo MS DSQ II, column DB 35-MS

capillary standard non-polar column, dimensions 30mts, ID is 0.25mm, Film is 0.25 µm,

carrier gas used is He and flow rate 1.0 ml/min. Oven temperature from 70 oC raised to 260
o
C at 6oC per min.

2.6 Diesel engine trial performance study

8
 Diesel engine trials were conducted on TurbochargedEicher E483 at a constantspeed.

The turbocharger system contains intercooler but no waste-gate. There is no EGR control

fitted in the engine. A schematic working layout of test engine set up is shown in Fig. S1 and

Table 1 shows the specifications of the test engine.

3. Results and Discussion

3.1 Characterisation of ZSM-5 Catalyst

The XRD patterns of the synthesized and commercial ZSM-5 zeolites are shown in

Fig. 2a. It is obvious from the figure that XRD pattern of the synthesized ZSM-5 seems to be

similar to those of XRD pattern of the commercial ZSM-5. This indicates that the synthesized

materials retain the crystal structure of ZSM-5. The Fig. 2b shows nitrogen

physisorptioncurve of the ZSM-5 exhibit a type IV isotherm. The BET values of the ZSM-5

was measured, the total surface area and pore volume of the ZSM-5 were measuredto be 346

m2/g and 0.39 cm3/g respectively. In addition to that, the material also possesses mesoporous

surface area and pore volume of (Smeso and Vmeso) 112.7 m2/g and 0.09 cm3/g,respectively.The

material shows a large hysteresis loop from P/P0 = 0.45 to 1 which is because of the presence

of mesoporosity. Hence, the materials possess both high mesoporous and moderate

microporous surface area. In order to understand the surface morphology of nonporous

ZSM-5, HR-TEM analyses have been carried out. HR-TEM images as shown in Fig.

2cdisplay the high crystallinity nature of from its lattice fringes in agreement with XRD result

which corresponds to the MFI structure. The TPD test was conducted for ZSM-5 to analyze

the acidic properties of the ZSM-5 zeolite catalyst. NH3-TPD technique was adopted to

evaluate the acidic properties. The TPD profile of the ZSM-5 zeolites is displayed in Fig. 2d.

The TPD profile of ZSM-5 zeolite has two desorption peaks observed around at 190 °C (low-

temperature peak) and 390 °C (high-temperature peak). The low-temperature peak is

attributed to the ammonia desorption from the weak acid sites and the high-temperature peak

9
is attributed to the ammonia desorption from the stronger acid sites (Brønsted and Lewis acid

sites) [24]. The total acidity is 1.45 (mmol/g), Lower temperature peak is 1.02 and the higher

temperature peak is 0.43.

3.2 Analysis of FE-SEMcharacterizationof ZSM-5

Field emission surface electronmicroscopy (FE-SEM), along with energy dispersive

spectroscopy (EDS) was done for ZSM-5 catalyst (25). Fig.3a shows 1µm and Fig.3bshows

2µm, resolution pics of the catalyst. The morphology of this catalyst is irregular slate and

hence unable to fix the average diameter of the particles. Fig.3c shows the material

composition of the catalyst. Fig.3d shows the element distribution map of the catalyst. The

element composition indicates the well-formed ZSM-5 catalyst and the distribution mapping

establishes the uniform presence of aluminosilicates.

Pyrolysis method of conversion of PP to liquid fuel facilitates the energy recovery

option. A furnace of 1.5KW rating provides the input energy requirement for the pyrolysis

reaction in this study, and if we assume the entire reaction is taking place at the maximum

rating, the energy input for the pyrolysis experiment is 8MJ/kg.The calorific value of the

pyrolysis product (PPO) is 43MJ/kg, and thus providing a net energy gain of 35MJ/kg. The

reaction time and temperature depend on the composition of the feedstock material. PP and

styrene had a reaction time of 30 mins, while HDPE and LDPE had a reaction time of 60

mins. HDPE and LDPE have a specific heat of 2.3KJ/kgK, whereas PP has a specific heat of

1.9 KJ/kgK. Lower specific heat implies lower heat required to increase the temperature of

the material. This can be a reason for lower reaction time and temperature for pyrolysis of PP

10
in comparison with HDPE and LDPE. Styrene had lower reaction time and temperature than

HDPE/LDPE as the compounds in styrene are mostly aromatic.

As shown in Fig.4a, the reaction time for PP was the lowest and same time the oil

yield was the highest for PP amongst the four selected plastics. PP gave a yield of 90% with a

ZSM-5 to PP ratio of 1:4. Elsewhere it was observed that catalytic pyrolysis using kaolin as a

catalyst with 1:3 ratio of catalyst to waste plastic yielded 87.5% oil [26]. Oil yield for styrene,

LDPE and HDPE were found to be 75,60, and 50 wt.% in their pyrolysis products,

respectively. Wax produced was filtered out of oil and measured. It was observed that PP had

negligible traces of wax, while styrene, LDPE and HDPE had 15, 25 and 25 wt.% in their

pyrolysis products, respectively. Gas and coke formed the balance of wt.% of the pyrolysis

products. Gas and coke for PP was 8% and followed by styrene, LDPE and HDPE having 10,

15 and 25wt.% respectively. It can be observed that PP gave higher yield with negligible wax

and remained stable throughout its storage life without forming gums and deposits. HDPE

and LDPE pyrolysis oil were unstable during its storage life and transformed completely into

wax.

Fig.4b shows the reaction temperature of PP as lower than the reaction temperature of

LDPE and HDPE. PP and styrene have a reaction temperature of350oC, while LDPE and

HDPE have a reaction temperature of 450oC.Lower reaction temperature, along with lower

reaction time, will enable lower cost of heating in favor of PP, thereby net energy savings

will be higher for PP conversion. The lower carbon molecules are easier to crack than higher

carbon chain molecules [27].

4.1 Physicochemical properties of pyrolysis oiland diesel

The results of physicochemical properties of produced pyrolysis oil are listed in Table

2 and compared with diesel physicochemical properties. The viscosity of fuel ensures proper

atomization in diesel engines [28]. Pour point and kinematic viscosity of PPO are closer to

11
diesel values. Pyrolysis oil of HDPE and LDPE have 400% and 200% higher kinematic

viscosity in comparison to diesel. Even though styrene has comparable viscosity with diesel,

its cetane value and conradson carbon residue values are not within the range of diesel values.

4.2 FT-IR Analysis

Fig.5 shows the FT-IR results of all the four types of produced pyrolysis oil and

diesel. The functional group of diesel shows the stretching of sp3 hybridized C-H compounds

at just below 3000 cm-1. There is no other stretching observed in the functional group which

implies the absence of sp2 hybridized C=H hydrocarbons. The FT-IR of produced pyrolysis

oil of PP, LDPE, HDPE, and styrene shows stretching of sp3 hybridized C-H compounds at

just below 3000cm-1 and presence of triple bond carbon compounds at 2200 to 2013 cm-1 and

sp2 Hybridised C=H compounds at stretching below 1785 cm-1.The FT-IR peaks of PPOwere

similar to the findings byR.Morent et al. [29]. FTIR findings confirm the presence of alkenes

in all the four types of produced pyrolysis oil. GC-MS results tabulated in this study further

confirms the results of FT-IR.

4.3 GC-MS analysis

Fig.S2 shows the GC graphs in the order of Diesel, PP, LDPE, HDPE, and styrene.

Table 3 shows the GC-MS of diesel. Table S1, S2, S3, and S4, shows the GC-MS results in

the order of PP, LDPE, HDPE, and styrene. GC-MS data of diesel is shown in Table 3 andthe

data shows that most of the chemical components in dieselarealkanes, benzene, and

naphthalene. Alkanes are about 50% of the concentration, benzene 28.81%, and naphthalene

13.73%. It was observed earlier by J.Erwin that diesel comprised 74% of saturates and 23.6%

aromatics [30]. GC-MS results of all thefour types of produced pyrolysis oil showthepresence

of alkanes, alkenes, and aromatics. TheGC-MS of all the four types ofproduced pyrolysis oil

12
shows the presence of alkenes and comparatively diesel has only traces of alkenes. Alkene

compounds are unsaturated double bonds, which cause high HRR during combustion in

diesel engines [31].

Fig.6ashows the GC-MS data arranged as per the carbon number range of alkane

compounds present in diesel andall the four types of produced pyrolysis oil. Diesel has

alkanes of about 33.13% in C10-C20 range and 10.13% in C20-C30 range. In comparison, the

producedpyrolysis oils have most of the alkanes in the C20-C30 range. The study shows the

presence of higher carbon number alkane compounds in produced pyrolysis fuel in

comparison to diesel. Amongst the four types of produced pyrolysis oil, PPO has all the

alkanes in C20-C30 range whereas LDPE, HDPE, and styrene have a concentration in C20-C30,

C30-C40, and even C40-C50range. This can be a reason for PPO having a lower viscosity than

LDPE and HDPE and hence suitable for injecting along with diesel in diesel engines.The

presence of higher carbon number compounds in pyrolysis oil results in higher CO and CO2

emission than diesel fuel.

Fig.6bshows the GC-MS data arranged as per the carbon number range of alkene

compounds present indiesel and all the four types of produced pyrolysis oil. Again, PPO has

alkenes in the lower carbon number range thanthe other three produced pyrolysis oil. PPO

has a lower carbon number of alkanes and as well as alkenes amongst the four plastics chosen

for this study. From GC-MS data it can be concluded that PPO has more diesel-like

characteristics amongst the four waste plastics selected for this study. Fig. 6c shows the GC-

MS data of aromatic compounds present in diesel and all the four types of produced pyrolysis

oil. Aromatic compounds in all the four produced pyrolysis oil are lesser than in diesel and

hence it can be used only as a blended fuel with diesel.

5. Combustion performance

5.1 Modelling of combustion performance of PPO

13
 Fuel Spray combustion of diesel engines involves complex chemical reactions.

Modeling on the basis of a single droplet is easy to understand the process of combustion.

The burning regression rate of a droplet determines the ignition and combustion

characteristics of fuel.

q” = ŕ ρfQV
where q” is the heat flux (KJ/m2.s) available at the surface of the droplet to vaporize the

droplet, ŕ is the regression rate of the droplet (m/s), ρf is the density of the fuel and QV is

theoverall heat of evaporation per kg of fuel. In the above equation, if the QV increases for the

same heat flux, then the regression rate of droplet reduces.Table S5 shows the latent heat of

vaporization of alkanes and alkenes arranged as per carbon number order[32-36]. The latent

heat of vaporization is almost doubling from C10 to C20 and also from C20 to C30. When

compared to diesel, PPO contains higher carbon number alkanes and alkenes, as shown in

GC-MS study. Thus, the higher carbon number of alkanes and alkenes in PPO will result in

higher latent heat of vaporization. This drastic increase in latent heat of vaporization will

result in delayed regression rate of burning and hence delayed and inefficient fuel combustion

of PPO. The deductions made from this modeling study are confirmed by the results of this

experimental study.

5.2 Cylinder pressure and heat release rate

Fig.7a and fig.7b show the values of cylinder pressure for both 100%and 75%load,

respectively. The peak pressure at 100% load for 5 PPO,10 PPO and 15 PPO are 3%, 5%, and

7%higher than diesel. The peak pressure at 75% load for 5PPO, 10 PPO and 15 PPO are 3%,

4%, and 6% higher than diesel. The difference remains the same at 100% and 75% loads.

Higher cylinder pressure is due to an increased delay period in the combustion of blended

fuels [37-38]. Ignition delay is an important factor in the combustion of fuels in diesel

engines. There are many qualitative and quantitative parameters influencing ignition delay.

14
The parameters which influence the results of this study are fuel type and air-fuel ratio. The

produced PPO fuel contains unsaturated compounds. The double bond nature of these

compounds requires higher energy for dissociation, which causes a delay in the combustion

of PPO. The ignition delay caused by blended fuels is predominantly chemical delay[39].The

chemical delay in droplet combustion can be attributed to the low burning regression rate (r)

of a droplet, which is normally determined by the rate of heat transfer from the surrounding

to the droplet surface. The burning regression rate is inversely proportional to the heat of

vaporization. The heat of vaporization comprises both latent heat of vaporization and as well

as sensible enthalpy. Taking only latent heat of vaporization into consideration, it can be said

that the burning regression rate (r) decreases with the increased latent heat of vaporization

(∆Hv). The carbon numbers of the majority of alkanes in diesel range from C10 to C20and the

latent heat of vaporization for the same range varies from 41.5 to 101.80 KJ/mol. This range

of latent heat of vaporization of alkanes in diesel can be compared to PPO. The carbon

number of majority of alkanes in PPO range from C21 to C30 and subsequently the latent heat

of vaporization for the same range varies from 109.4 to 162.2 KJ/mol. It can be observed that

the average latent heat of vaporization of alkanes in PPO is 80% higher than the vaporization

values of alkanes in diesel. This increase in latent heat of vaporization can be the reason for

delayed combustion and subsequent high heat release rate in the diffusion flame stage.This

can be solved by hydrocracking the pyrolysis oil to lower carbon number compounds. An

attempt can also be made to install a higher efficiency turbocharger, which can deliver higher

air deliveryfor the same amount of fuel being burnt.Ignition delay period can be observed as

5° of crank angle for 15 PPO blended fuel. Delay period increases with higher blending ratios

and this reflects in increased cylinder pressure for higher blending ratios.

Fig. 8a and Fig. 8b,indicate the HRR of diesel and blended fuel for 100% and 75%

load, respectively.TheHRR at 100% load for 5 PPO, 10 PPO, and 15 PPO is 0%, 7%, and

15
14% higher than diesel. The HRR when compared to diesel at 75% load for 5 PPO, 10 PPO

and 15 PPO is0%, 60%, and 80% higher than diesel. At 5% the HRR is the same as diesel,

but as blend ratios increased, the HRR increased at a higher rate. High HRR is due to the

presence of double bond alkene compounds in PPO. The double bond structure of these

compounds releases much higher dissociation energy than single bonds. The presence of

double bonds leads to combustion delay. Combustion delay causes inefficient

combustion[40].The delayed combustion is visible in the premixed combustion zone, and the

same gets extended further for higher PPO blend ratio. The delayed combustion results in

high HRR extending into the diffusion combustion zone.Comparison of heat release between

100% and 75% gives interesting variation facts. The HRR at 75% load for 10 PPO and 15

PPO are substantially higher than 100% load.

5.3 Engine Performance

The calorific value of PPO is slightly lesser than diesel. PPO has higher carbon

number compounds. The density of decane (C10H22) is 730 kg/m3, while that of octadecane

(C18H38) is 777 kg/m3. It is known that the rate of premixed combustion is proportional to the

mass of the fuel-air mixture. The increase inthe mass of the fuel-air mixture due to higher

density compounds in PPO will result in a higher heat release rate during combustion. The

higher HRR with delayed combustion increases the exhaust temperature and thermal losses.

Brake thermal efficiency (BTE)reduces due to lower calorific value and thermal losses. The

BTE as shown in Fig.9ais decreasing with increasing blend ratios. Diesel shows a maximum

efficiency of 35%, whereas 15 PPO shows a maximum efficiency of 28%. 5 PPO has BTE a

little closer to diesel values. Brake specific fuel consumption (BSFC), as shown in Fig.9bis

increasing with higher blends. BSFC is higher at part loads than full load. Turbocharger runs

at lesser efficiency at part loads and this is one reason for inefficient combustion of blended

16
fuels which have higher carbon number compounds.BSFC for 15 PPO at part loads is 20%

more than diesel, whereas at full load it is only 10%. BSFC for 5 PPO is 10% more at part

loads and almost same as diesel at full load. Exhaust gas temperature is shown in Fig. 9c. The

Exhaust temperatures at 50% load for 5 PPO, 10 PPO, 15 PPO were 14%, 16%, 17% higher

than diesel. Exhaust temperature at 100% load for 5 PPO, 10 PPO, and 15 PPO were 15%,

18%, 20% higher than diesel. Higher HRR results in higher thermal losses by increased

exhaust temperature.

5.4 Exhaust emission results

Fig.9d shows the COlevels of diesel and blended fuels. CO is a product formed due to

insufficient air for complete combustion. CO emission levels were significantly higher than

diesel at partial engine loads and almost close to diesel at full load. At50% engine loads the

CO emission for 5 PPO, 10 PPO, and 15 PPO are200%, 300%, and 400% higher than diesel

values. At 100% engine load the CO levels for 5 PPO, 10 PPO, and 15 PPO are almost the

same as diesel values. It has been observed that PPO has higher carbon number compounds

than diesel. These higher carbon molecules need a higher amount of oxygen for complete

combustion.At part loads, the efficiency of aturbocharger is much lower than at full loads.

This results in insufficient air for the blended fuel, which has higher carbon number

molecules. Hydrocracked PPO will result in lower CO emissions.

Fig. 10a shows the carbon dioxide (CO2) levels of PPO blends at lower loads are

slightly higher than diesel but the difference increases with load. At partial loads, the CO2

levels for 5 PPO, 10 PPO, and 15 PPO are 22%, 26%, and 33% higher than diesel. At full

engine loads, the CO2 levels for 5 PPO, 10 PPO, and 15 PPO are 40%, 45%, and 50% higher

than diesel. The increase in CO2 emission can be attributed to two factors. First, the presence

of higher carbon number compounds in blended fuel than diesel. At full load, the

17
turbocharger gives a higher amount of excess air and this result in combustion of excess

carbon. Second,the higher fuel consumption which results from lower BTE.

Fig. 10b shows the NOx levelsfor diesel and blended fuels.NOx is formed in diesel

engines by thermal mechanism and to an extent bythe prompt mechanism. The thermal

mechanism gives anexponential increase in NOx values at higher temperatures.The maximum

adiabatic flame temperature for a particular fuel and aircombination occurs with a

stoichiometric mixture. The quantity of excess air can be part of the design to control the

adiabatic flame temperature. PPO has higher carbon number compounds and hence the

excess air availability reduces. The reduction in excess air availability results in higher

temperatures and hence causes an increase in NOx. PPO blended with diesel has the potential

of having cylinder combustion temperatures higher than pure diesel due to combustion delay

phase and subsequently higher heat release rate in the diffusion phase. PPO and diesel blends

alter the air-fuel ratio designed for pure diesel run. The increased carbon number elements in

PPO will make the air-fuel ratio richer than the designed equivalence ratio. A richer fuel will

tend to have a higher thermal load on the engine and thereby cause higher NOx due to thermal

mechanism. Thus, it is possible to have a higher level of NOx under a thermal mechanism

caused by delayed combustion and as well as due to rich fuel. Again, the higher carbon

number elements in PPO may assist the prompt mechanism to increase NOx formation. Thus,

both thermal mechanism and as well as prompt mechanism have the potential of higher NOx

values for PPO and diesel blends. The solution for reducing NOxis possible if the combustion

delay is reduced and as well as by providing a correctly designed air-fuel ratio.The increase

in NOx is observed to be higher at partial loads and lesser at full loads. At 50% engine

loadthe NOx levels for 5 PPO, 10 PPO, and 15 PPO are 27%, 38%, and 50% higher than

diesel. At 100% engine load the NOx levels for 5 PPO, 10 PPO, and 15 PPO are 12%,

21%,and 26% higher than diesel.PPO obtained through thermal pyrolysis showed higher NOx

18
levels over the entire load range [41]. Exhaust gas recirculation (EGR) has resulted in a

reduction in NOx in biodiesels and waste plastics[42-43]. Using EGR may result in NOx

reduction, but it also slightly reduces the BTE.

Fig.10cshows the emission levels of unburned HC emissions. UnburnedHC emissions

are a result of incomplete combustion. Combustion delay, the insufficient air-fuel ratio for the

blended fuel and the possibility of spray pattern disturbed by the slightly lower viscosity of

PPO are some of the reasons for unburnedHC emissions. At 50% load, the unburnt HC for 5

PPO, 10 PPO, and 15 PPO are 30%, 100%, and 123% higher than diesel. At 100% load, the

unburnt HC for 5 PPO, 10 PPO and 15 PPO are35%, 80% and 90%, respectively.It has been

observed earlier that mixed waste plastic pyrolysis oil showed higher unburnedHC [44].

Unsaturated double bond compounds and higher carbon number compounds are not easily

combustible,which leads to a significant increase in HC emissions in exhaust [45]. An

increase in HC using PPO as fuel has been reported earlier by IoannisKalargariset al.[46].

Increased delay period and high HRR have been reported earlier by Vishwanath K.Kaimal et

al.[47]. Increased delay period during combustion and higher HRR are caused by the

unsaturated compounds in PPO.

6. Relationship between the ZSM-5 properties and the pyrolysis results

The ZSM-5 zeolite catalyst plays a crucial role in the pyrolysis of plastic wastes

reaction. Without a catalyst, pyrolysis of plastic wastes yielded yellow colored oil for LDPE,

HDPE and PP and brown color for PS. Catalytic decomposition associated with the PSW

found a slight impact on the oil color. Also, Panda and his coworker Singh observed that the

oil color collected in PP catalytic pyrolysis employing alumina, silica, and in addition kaolin

as catalysts were yellow in color [48]. In our work, we found a considerable difference in

change of color. The oil yield considerably increased with the presence of a catalyst in

comparison to without any catalytic systems. The utilization of a catalyst increased the

19
capability to crack or decompose the polymer, as a consequence improving the more liquid

product ultimately. Lopez and his collaborators utilized red mud and ZSM-5 as catalysts in

the PSW pyrolysis and revealed that the maximum yield of liquid were 76.2 and 56.9 wt%,

correspondingly [49]. We also observed more yield of liquid products after the use of

catalyst.

The benefits of the present pyrolysis system are that lesser quantity of wax (negligible

traces) of wax for PPO and char are developed throughout the method. This can be explained

that the ZSM-5 catalyst acidic nature that can facilitate the cracking or decomposition of

waxes into lighter products. The highly acidic catalyst (low SiO2/Al2O3 ratio) seemed to be

considerably effective in cracking of waxes when compared with the significantly less acidic

catalyst (high SiO2/Al2O3 ratio) [50]. Also, in our present studies, we obtain less amount of

wax products, which indicates that the present catalytic system (ZSM-5) sufficiently acidic

and effectively convert cracking of waxes into liquid products. Pyrolysis reaction without any

catalyst produces pyrolysis-oils which can undergo polymerization to produce solid

materials. When compared to pyrolysis reaction without the presence of catalysts, the

pyrolysis-oil products were low viscous liquids subjected to catalytic conditions, revealing

the superior cracking and breakdown of plastic wastes into liquid hydrocarbons (low

molecular weight). The pyrolysis reaction time in this current work was considerably shorter.

From the above discussions, it is clear that the pyrolysis results strongly depend on the ZSM-

5 properties.

7. Conclusion

Experimental methods were adopted to find the suitability of PSW pyrolysis oil for

conversion to diesel. The selected waste plastics for pyrolysis are HDPE, LDPE, PP, and

styrene as these four materials comprised 65% of the plastics in use. PPO had

physicochemical properties closer to diesel values. Viscosity is an important factor in

20
atomization of fuel in diesel engines, and PPO had a viscosity in the range of diesel

value.Pyrolysis oil of styrene had a viscosity similar to PPO, but its calculated cetane index

was not within the diesel values, and hence, it was not suitable as diesel fuel. The FT-IR and

GC-MS data confirmed the presence of lower carbon number molecules forPPO when

compared to the other produced pyrolysis oil. The lower carbon number of PPO is one of the

reasons for its viscosity to be lower than other plastics. PPO was selected amongst the

pyrolysis oil of four selected plastics for diesel engine trials. PPO blended with diesel showed

higher peak pressure and HRR than diesel. The CO, NOx and HC emissions of blended oil

were significantly higher than pure diesel. The higher carbon number of alkanes and the

presence of alkenes in PPO cause higher emissions and ahigher HRR. The double bond

nature of these unsaturated compounds results in higher HRR, increased combustion delay

and lower BTE in diesel engines.PPO blends with diesel have not given favorable results for

the efficient and environmentally safe operation of diesel engines. In this conclusion, we

stress the fact that the presence of unsaturated compounds and higher carbon number

saturated compounds in PPO preventfrom getting diesel-like combustion results. The strategy

of future research should be to reach the objective of net energy recovery from after use

plastics by meeting the emission standards of legislation.

7. Future Research

We have further taken up experimental studies to hydrogenate PPO in the presence of

various catalysts to convert the alkenes present in PPO to alkanes. Hydrogenation will

alsoassist in cracking the higher carbon number compounds to lower carbon number range.

The engine trial results of hydrogenated PPO blended with diesel will be published soon.

Such conversion due to hydrogenation should improvethe combustion of the produced fuel in

diesel engine and reduce emissions.

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28
 Tables

Table 1. Test Engine Specifications

Diesel Engine Type 4 cylinder in-line T/C, DI

Compression ratio 17.5:1

Displacement 3298 cm3
Max. power 70 kW
Turbocharger Boost pressure
Injector: hole _ dia 5 _ 0.209 mm
Injection timing 12 deg. CA btdc
Nozzle opening pr 23 MPa
Bore x Stroke 100 mm x 105mm

Table 2. Physicochemical properties of waste plastic pyrolysis oil and diesel

Parameter Name Diesel HDPE LDPE Polypropylene Styrene Unit Method

Density @150C 0.8375 0.7999 0.7985 0.7714 0.9405 gm/ml IS;1448(Part 16)
0
Pour Point < -15 +24 + 26 < -30 < -30 C IS;1448(Part 10)
0
Flash Point 72 24 20 20 32 C IS;1448(Part 21)
0
Fire Point 82 34 30 30 42 C IS;1448(Part 21)
Calculated Cetane 52 65 68 60 10 N/A IS;1448(Part 9)
Index
Kinematic 2.61 10.12 4.98 1.72 1.83 cst IS;1448(Part 25)
Viscosity at 400C
Gross Calorific 10897 11042 11,507 10,745 9288 Kcals/k Bomb Calorimeter
Value g
Ash Content 0.01 0.03 0.01 0.01 0.01 % IS;1448(Part 16)
Conradson Carbon 0.18 0.37 0.06 0.10 1.38 % IS;1448(Part 16)
Residue

1
Table 3. Mass Spectrometry of Diesel

RT Time Compound Chemical Formula % Area

3.45 Benzene Diethyl C10H14 5.11

3.76 Benzene Dimethyl C8H10 3.33
5.18 Benzene Trimethyl C9H12 5.64
6.14 Benzene Diethyl C10H14 5.11
7.69 Benzene Dimethyl C8H10 9.25
8.22 Dodecane C12H26 8.31
9.30 Naphthalene, Methyl C11H14 3.57
9.66 Dodecane C12H26 4.82
10.13 Napthalene, dimethyl C12H16 4.77
11.40 Tetradecane C14H30 4.09
12.60 Napthalene, trimethyl C13H18 3.23
13.45 Pentadecane C15H32 3.92
15.59 Hexadecane C16H34 3.46
17.73 Octadecane C18H38 3.81
19.83 Octadecane C18H38 3.64

2
Figure 1.

Figure 1.Layout diagram of Pyrolysis Unit.

Figure 2.

Figure 2.Catalyst Characterisation

Figure 2a. shows XRD patterns, Figure 2b. shows BET Isotherm, Figure 2c. shows HR-
TEM image, and Figure 2d.shows TPD analysis of synthesised ZSM-5 Catalyst.
Figure 3.

Figure 3a.1µm resolution FE-SEM pic of synthesised ZSM-5,Figure 3b. 2µm resolution
FESEM pic of synthesised ZSM-5,Figure 3c. Element composition of synthesised ZSM-5
and Figure 3d.Element distribution map of ZSM-5.
Figure 4.

Figure 4a. Pyrolysis reaction results and Figure 4b.Results of Pyrolysis reaction

temperature.

Figure 5.

Figure 5. FT-IR Spectra of a) Styrene b) PP c) LDPE d) HDPE and d) Diesel.

Figure 6.

Figure 6a. Carbon number range of alkane products of produced pyrolysis oil and diesel,
Figure 6b. Carbon number range of alkene products of produced pyrolysis oil and diesel, and
Figure 6c.Composition of aromatic products of produced pyrolysis oil and diesel.
Figure 7.

Figure 7.Variation of cylinder pressure for a) 100% load and b) 75% load.

Figure 8.

Figure 8. Variation of heat release rate for a) 100% load and b) 75% load.
Figure 9.

Figure 9a.Variation of BTE with load, Figure 9b.Variation of BSFC with load, Figure

9c.Variation of exhaust gas temperature with load, and Figure 9d.Variation of carbon

monoxide emission with load.

Figure 10.

Figure 10a. Variation of carbon dioxide emission with load, Figure 10b.Variation of oxides
of nitrogen emission with load, and Figure 10c.Variation of unburned hydrocarbon emission
with load.
Scheme1.

Scheme 1. Shows process methodology of waste plastic to diesel fuel

Highlights
• Four types of plastics selected to determine which plastic has a diesel like quality.

• Physicochemical properties, FTIR, GCMS results showed Polypropylene had diesel like
qualities.

• Diesel Engine trials done with polypropylene pyrolysis oil blended with diesel as fuel.

• Engine trial results showed delayed combustion, high heat release rate and higher emission.