Waste Management 77 (2018) 114–130

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Production of benzene/toluene/ethyl benzene/xylene (BTEX) via

multiphase catalytic pyrolysis of hazardous waste polyethylene using
low cost fly ash synthesized natural catalyst
Pramendra Gaurh, Hiralal Pramanik ⇑
Department of Chemical Engineering and Technology, Indian Institute of Technology (Banaras Hindu University), Varanasi, Uttar Pradesh, India

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

Article history: The valuable aromatics benzene, toluene, ethyl benzene and xylene (BTEX) were effectively produced
Received 10 February 2018 from waste polyethylene (PE) using fly ash synthesized catalyst. The BTEX yield was enhanced signifi-
Revised 4 May 2018 cantly using multiphase catalytic pyrolysis of polyethylene. Low cost natural catalyst was synthesized
Accepted 8 May 2018
from fly ash (FA) in 5 different synthesized form i.e., fly ash in natural form (FAN), fly ash calcined at
Available online 12 May 2018
600 °C (FA-600), 700 °C (FA-700), 800 °C (FA-800) and 900 °C (FA-900). The thermal and catalytic pyrol-
ysis both were conducted in a specially designed semi-batch reactor at the temperature range of 500–800
Keywords:
°C. Catalytic pyrolysis were performed in two different phases within the reactor batch by batch system-
Fly ash
GC-FID
atically, keeping the catalyst in a liquid phase (A-Type) and liquid and vapor phase/multiphase (B-Type),
BTEX respectively. The maximum liquid yield of 78.20 wt% was obtained at a temperature of 700 °C using FA-
Multiphase pyrolysis 800 catalyst in A-type arrangement. Total aromatics (BTEX) of 10.92 wt% was obtained for thermal pyrol-
Polyethylene ysis at a temperature of 700 °C. In contrary, the aromatic (BTEX) contents were significantly increased for
the catalytic pyrolysis in both reactor arrangement A and B types, nearly doubled from 10.92 wt% (ther-
mal pyrolysis) to 21.34 wt% for A-type and 22.12 wt% for B type/multiphase. The pyrolysis oil was char-
acterized using GC-FID, carbon residue test and other fuel testing methods to evaluate the suitability of
its end use and aromatic content.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction and waste polyethylene as feed material for the catalytic pyrolysis,
which eventually reduces the environmental pollution problem
Silica and alumina (Si/Al) based ZSM-5 is widely used catalyst in and thus, protects mother earth.
cracking, isomerization and aromatization of larger hydrocarbon Catalytic pyrolysis is a chemical recycling method that involves
molecules due to its excellent catalytic properties, thermal stability the conversion of polymers to recover useful products could be the
and acidity (Gaurh and Pramanik, 2018). ZSM-5 is commercially appropriate route (Malkow, 2004; Shent et al., 1999). So far, many
available costly catalyst and thus, the use of this catalysts in selec- articles have been published on catalytic conversion of different
tive catalytic cracking of high molecular petroleum products and types of plastics and polymers to different products, including
different types of polymers e.g., polyethylene (PE), poly propylene chemicals and fuels on different types of catalysts (Lin et al.,
(PP), and poly styrene (PS) will add cost to entire process in man- 1998; Lin et al., 2010). Among them, mostly focused on the cat-
ufacturing of valuable marketable products like benzene, toluene, alytic conversion of plastic wastes using different types of catalysts
ethyl benzene and xylene (BTEX). However, many scientists have to improve the quality of liquid oil (Wang and Wang, 2011). The
tested laboratory synthesized catalyst e.g., mordenite, clay, red catalysts include red mud (Lopez et al., 2011a), FCC (Lee, 2009),
mud, natural zeolite for the catalytic pyrolysis of wastes plastics ZSM-5 (Gaurh and Pramanik, 2018; Lopez et al., 2011a), HZSM-5
(Chen et al., 2014). As we know that the selection of catalyst and (Hernandez et al., 2007), Y-zeolite (Lee, 2012), Fe2O3 (Sarker and
raw material both are very important to get the desired products Rashid, 2013), Al2O3, Ca(OH)2 (Sarker et al., 2011) and natural zeo-
by means of catalytic pyrolysis. Here, our research focuses on the lite (Miandad et al., 2017; Syamsiro et al., 2014). The key role of
utilization of hazardous waste materials, like fly ash as a catalyst catalysts was to increase the lighter fractions in the liquid oil such
as gasoline (Lerici et al., 2015), and decrease the overall process
energy inputs (Lopez et al., 2011a). For instance, the use of ZSM-
⇑ Corresponding author.
5 catalyst decreased the impurities such as solid residue, sulphur,
E-mail address: hpramanik.che@itbhu.ac.in (H. Pramanik).

https://doi.org/10.1016/j.wasman.2018.05.013
0956-053X/Ó 2018 Elsevier Ltd. All rights reserved.
 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130 115

nitrogen, and phosphorous in the produced liquid oil (Miskolczi Table 2

et al., 2009). It is well known that the use of catalysts with a high Fly Ash utilization in India 2015–16.

BET surface area provides more interaction between reactants and Mode of fly ash utilization Wt. (%)
the catalyst surface, resulting in an increased rate of cracking reac- Cement 41.97
tion to produce more gases than liquid oil (Syamsiro et al., 2014). Bricks and Tiles 12.85
Substantial research is underway to explore different types of cat- Reclamation of low laying area 11.21
alysts and their dynamic role in the pyrolysis process and its prod- Mine filling 10.91
Ash dyke raising 7.67
ucts. Different types of catalysts such as FCC (Achilias et al., 2007), Others 7.32
spent FCC (Lee, 2009), HZSM-5 (Lee, 2012), ZSM-5 (Lopez et al., Roads and flyovers 4.87
2011b;Miskolczi et al., 2009), Cu-Al2O3 (Adnan et al., 2014), Agriculture 2.15
CoMo/Z (Sriningsih et al., 2014), Zeolite-ß (Ojha and Vinu, 2015), Concrete 1.00
Hydro power sector 0.04
natural zeolite (NZ) (Syamsiro et al., 2014), Red Mud (Lopez
et al., 2011a), Al(OH)3 Ca(OH)2 (Sarker et al., 2011) and Fe2O3
(Sarker and Rashid, 2013) have been used extensively to enhance
the yield and quality of the products. Table 3
Chemical composition of fly ash.
It is clear from the above literature survey that there is a still
scope of manufacture catalyst from many natural solid wastes for Components Wt. (%)
the catalytic cracking of plastic wastes, mainly polyethylene (PE) SiO2 53.56
due to its uncontrolled and excessive use. In this context, haz- Al2O3 27.71
ardous solid waste of thermal power plant i.e., ‘‘fly ash” could be Fe2O3 5.53
MgO 0.91
used as catalyst material which is a rich source of natural silica CaO 4.50
and alumina those are trapped in the fuel coal from its origin. K2O 0.94
Fly ash is the main combustion by-product of coal fired power Na2O 0.37
plants and a huge amount of fly ash is produced by the almost all Others 6.48
Ignition loss 5.88
developed and developing countries as reported by Earth science
reviews (Ram and Masto, 2014) (Table 1). Unfortunately, more than
half of fly ash is disposed of in land filling because it finds no other ethyl benzene and xylene (BTEX). In addition, plastic waste poly-
suitable and economical application. The huge production of fly ash ethylene is nightmare for all the developing countries. This paper
is extremely worrying because of the unplanned disposal. In India, explores the scope of waste polyethylene management using waste
fly ash (FA) is being generated at the rate of nearly 132 million ton- fly ash as a natural catalyst resulting in valuable aromatics/BTEX.
nes per annum (MTPA) from thermal power plants in 2011–12 As we know, used polyethylene accounts major portion of the
(Table 1). There are serious environmental health hazards associ- plastic wastes which is the key fraction of municipal solid wastes
ated with fly ash. In addition, the land requirement envisaged for (Gaurh and Pramanik, 2018). World’s oldest living holy city Vara-
disposal of fly ash is about 50,000 acre, with an annual expenditure nasi, India is severely affected by this waste polyethylene
of about Rs. 500 million for transportation. These problems clearly (Srivastava et al., 2014). The polyethylene creates several problems
spell out the fact that utilization of fly ash is absolutely essential. As which are (i) water logging due to blockage in city drainage system
a consequence, several investigations have been carried out in order (ii) animals mainly Cow in many occasions dyes as they eat poly-
to exploit this waste material into value added material. Over the ethylene when it is thrown with waste food stuff and (iii) contam-
last few years, fly ash has been gaining ground in finding solutions inate soil and water body as polyethylene is non-biodegradable. In
to environmental problems using it as an active ingredient in a nutshell, polyethylene is a hazardous material for the environ-
cement manufacturing and brick making, which is not sufficient ment and living being (Al-Salem et al., 2009). Keeping in mind
(Table 2) (The Gazette of India, 2016). the problems of holy city Varanasi, India due to the dumping of
Due to unique composition of fly ash (Table 3) (Malik et al., huge amount of solid wastes polyethylene, it was selected as a
2016) i.e., quartz, mullite, subordinately hematite and magnetite, raw material for the conversion of waste PE to valuable aromatics
carbon, and a prevalent phase of amorphous alumino silicate BTEX.
(Bayat, 1998; Hall and Livingston, 2002; Hower et al., 1996; Park et al., 2002 derived hydrocarbons (HC) using pyrolysis of
Koukouzas et al., 2006; Kukier et al., 2003; Mishra et al., 2003; different plastic wastes such as HDPE, LDPE. PP (Hwang et al.,
Sokol et al., 2000) makes fly ash an important source material in 2002; Hwang et al., 2014) and PS (Bagri and Williams, 2002a;
zeolite synthesis. Kim et al., 2002) contains low carbon chain compounds including,
Moreover, it is seen in the Table 1 that for the countries like gasoline range HCs in comparison to thermal pyrolysis (Scott et al.,
India, China, USA, Japan, Canada etc. a large amount of fly ash is 1990; Park et al., 1999; Aguado et al., 2000). Moreover, the cata-
unutilized. Thus, this paper focuses on the effective use of waste lysts increase the gaseous fraction and reduce the liquid oil yield
fly ash as a natural catalyst for the conversion of solid waste mainly when compared to thermal pyrolysis (Park et al., 1999; Beltrame
polyethylene (PE) to valuable hydrocarbons like benzene, toluene, et al., 1989). Furthermore, the conversion rate was increased at

Table 1
Country wise fly ash production and utilization.

Country Year FA generation (million tons) FA utilization (million tons) FA utilizationV (%)
India 2010–11 131.9 73.13 55.79
China 2010 480 321.6 67.0
USA 2011 59.9 22.98 38.36
Australia 2008 14.50 4.584 32.0
Japan 2006 10.96 10.65 97.2
Canada 2007–08 6.087 1.881 31
Israel 2012 1.445 1.359 94.05
Germany 2010 15.26 15.26 100
Turkey 2012 24.0 2.4 10
116 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130

low temperature in catalytic conditions in comparison to thermal collected fly ash was thoroughly washed with water to remove
pyrolysis (Park et al., 1999; Ding et al., 1997; Lee, 2001). Chung mud, dirt and any other suspended impurities before the calcina-
et al., 2003 studied on pyrolysis of polyethylene (PE) and tion of fly ash. The washed fly ash was then dried in an oven for
polypropylene (PP) using fly ash treated with NaOH as a catalyst. overnight at a temperature of 108 °C to remove moisture. Dried
No such detail study was performed in terms of catalysts prepara- fly ash was screened through a sieve of mesh size 230 (A.S.T.M.)
tion, characterization and product yield analyzes etc. [240B.S.S. or 63 mm] to remove the unburnt carbon and larger par-
Till date no research has been carried out on the BTEX produc- ticles. A fraction of the resulted raw fly ash without calcination was
tion from waste polyethylene using fly ash as a cheap and natural used in the pyrolysis process and designated as ‘‘FAN” i.e.,
catalyst. The BTEX were chosen as a target/ideal product here, untreated fly ash. The remaining of part of the washed and dried
since they have numerous applications, like benzene is primarily fly ash was calcined in order to improve physicochemical proper-
used as raw material for ethyl benzene to styrene and cumene to ties of synthesized catalysts in terms of BET surface area and Si/
phenol production. The third largest use of benzene is in the pro- Al ratio. The fly ash was calcined in a muffle furnace at four differ-
duction of cyclohexane, a nylon precursor. Toluene, the second ent temperatures i.e., 600 °C, 700 °C, 800 °C and 900 °C in static air
largest aromatic in BTEX/Hydrotreated Pygas (HPG), is used in for 5 h in which improved surface area of the FA catalyst and sur-
refinery streams such as gasoline blending for improvement of face Si/Al ratio followed by removal of sulfur and other impurities.
octane value. Ethyl benzene is widely used in industrial processes The calcined fly ash catalysts were designated as FA-600 (calcined
for the manufacture of styrene, which is then used for polystyr- at 600 °C), FA-700 (calcined at 700 °C), FA-800 (calcined at 800 °C)
ene manufacture. Ethyl benzene is also present as a solvent in and FAN-900 (calcined at 900 °C). All the catalysts were character-
inks, dyes and in petrol. Xylene is widely used in the production ized using SEM-EDX, FTIR and BET analysis to check the suitability
of plastic bottles and polyester clothing and as a solvent with a of utilizing it as catalysts for the pyrolysis of waste polyethylene.
range of applications from circuit board cleaning to thinning
paints and varnishes. Xylene may either be used in refinery 2.3. Experimental set up and method
streams for gasoline blending or further separated by isomers
for chemical applications (Thongplang, 2016). This research Fig. 1 shows the schematic of experimental set up of pyrolysis
explores the opportunities to utilize hazardous waste material process consists of a semi batch reactor. The treated and shredded
polyethylene and fly ash both in the effective and efficient way. waste plastic polyethylene (PE) sample of 50 g was fed to the reac-
Thus, the main aim of the present study was to synthesize low tor made of mild steel of 123 mm outer diameter, 112 mm inner
cost silica-alumina based catalyst from fly ash and systematically diameter and 135 mm height. The reactor was then properly sealed
investigate the effect of different process parameters e.g., operat- with a gasket to prevent the products leakage. The dimension of the
ing temperature, reaction time and batch by batch catalytic and reactor was fixed based on standard design criterion of appropriate
thermal pyrolysis to achieve maximum aromatics BTEX yield. L/D ratio of 1.2. This improves vapor recirculation inside the reactor
The synthesized catalysts were thoroughly characterized and and minimizes pressure drop. The thermal pyrolysis was performed
the pyrolysis products were systematically analyzed using GC- in the reactor arrangement as shown in Fig. 2a. A catalyst bed
FID, flash and fire point, calorific value (CV) test and carbon resi- (Fig. 2b and c) of FA was installed in the liquid phase (A-type) or
due to check the suitability of pyrolysis oil for the IC engine and both, liquid and vapor phase (B-type)/multiphase to perform pyrol-
other commercial uses. ysis of PE batch by batch, respectively. A porous stainless-steel plate
was used to support the FA catalyst as shown in Fig. 3a-b. A thin
layer of ceramic wool was used to make the catalyst bed through
2. Experimental
which vapor of hydrocarbons and gases could easily diffuse with
a better catalyst-vapor interaction (Gaurh and Pramanik, 2018).
2.1. Raw materials
The nitrogen gas was fed into the reactor at the rate of 10 mL/
min to ensure there is no oxygen and to maintain inert atmosphere
Municipal solid waste of Varanasi city, India comprises maxi-
inside the reactor. Adequate precautions were taken to make sure
mum food waste (31.9%) followed by plastic (22%), textile
that there is no leakage before we start the experiment. The ther-
(10.6%), paper (9.6%), glass (6.7%), cardboard (6.2%), ash (5.3%),
mal pyrolysis of PE were performed at different temperatures 500
leather (5.7%) and minimum metals waste (2.8%). Per capita
°C, 600 °C, 700 °C and 800 °C, respectively. The times for each set of
MSW waste generation rate is 800 MT per day, 0.217 kg/person/-
experiments were maintained for 35 min. Catalytic pyrolysis was
day in Varanasi city, India (Srivastava et al., 2014). The published
performed at feed to catalyst ratio of 20:1 using similar operating
literature shows that the plastic waste polyethylene contributes
conditions as that of thermal pyrolysis. During the reaction, the gas
nearly 41.5 wt% of municipal plastic waste. In view of this, the
and vapor mixture was allowed to pass through a copper tube con-
raw material waste polyethylene (PE) was collected from the
denser followed by an ice bath to decrease the vapor temperature
municipal dumping zone of Varanasi city. The PE waste, mostly
gradually and reduce the vapor loss at the gas collecting end. The
‘‘carry bag” was first subjected to water washing and dried in open
tube was covered with wet jute to enhance the rate of vapor cool-
sunlight. The dried polyethylene was cut into small pieces using
ing. Two conical flasks in series were kept in the ice bath and pyrol-
scissors manually. The average size of the cut polyethylene pieces
ysis oil was collected as condensate. The produced gas was trapped
used in the experiment was 4 mm
4 mm. This was done to
using gas holder. The solid residue was collected from the bottom
increase the heat transfer surface area of the material during the
of reactor after completion and cooling of each batch of experi-
melting process. The fly ash sample was collected from the Panki
ment. The produced gas was trapped using gas holder at the
thermal power plant, Kanpur India to synthesize catalyst from
extreme end of ice bath condenser. The liquid, gas and solid yields
the natural waste material. The bituminous coal is used as fuel at
were calculated using following Eqs. (1)–(3):
Panki thermal power plant.

wt:ofliquid
LiquidYield ¼
100 ð1Þ
wt:oftotalfeed
2.2. Catalyst preparation


wt:ofgas
The catalyst was synthesized from waste fly ash (FA) which was GasYield ¼
100 ð2Þ
collected from the Panki thermal power plant in Kanpur, India. The wt:oftotalfeed
 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130 117

Fig. 1. Schematic of experimental set-up.

Fig. 2. Reactor set-up of (a) thermal pyrolysis, (b) A-type (catalyst in liquid phase) and (c) B-type (catalyst in both liquid and vapor phase).


wt:ofsolid 51-ADD0048. Specific surface area and pore volume of synthesized
SolidYield ¼
100 ð3Þ
wt:oftotalfeed catalysts were analyzed using smart sorb 92/93 surface area ana-
lyzer using nitrogen physisorption at liquid nitrogen temperature.
where wt. of gas = [wt. of total feed  (wt. of liquid + wt. of solid)] FTIR analysis was carried out with Thermo-Nicolet 5700 model.
(Gaurh and Pramanik, 2018). The Ominc software was used to correct the medium’s background
material used during analysis. Fourier transformed infrared spec-
trophotometer was set to a resolution of 4 cm1, in the range of
2.4. Catalyst characterization
500–4000 cm1 using Nujol mull as reference.
The analysis of particle size and surface morphology of FA cat-
alysts like FAN, FA-600, FA-700, FA-800 and FA-900 were done 2.5. Analysis of the reaction products
by Scanning Electron Microscopy (SEM) and Energy Dispersive
Spectroscopy (EDS). The SEM-EDS were recorded on ZEISS EVO The compositional analysis of pyrolysis oil was evaluated by gas
18 SEM coating of quorum Q150R ES having model number chromatograph (NUCON 5765) using flame ionization detector (FID)
118 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130

with a SE-30 10% chromosorb W packed stainless-steel column (2 m pyrolysis oil is calculated using the oil sample specific gravity,

2 mm) (Raj et al., 2005). Flash and fire point of pyrolysis oil were which is the ratio of density of oil to that of water
obtained using Cleveland open cup apparatus (ASTM D 92). Carbon :TheAPIgrav ityofthepyrolysisoilsamplewascalculatedbythefollowing
residue of pyrolysis oil was obtained using Rams bottom Carbon equation. The API gravity of the pyrolysis oil sample was calculated
Residue Apparatus (IP 14/65). The density of pyrolysis-oil was mea- by the following equation (4):
sured according to ASTM D 1298 standard method. The API gravity of !
141:5
Deg: API ¼  131:5 ð4Þ
qpyrolysisoil

where qpyrolysis oil = specific gravity of fraction at ð (Tiab and

Donaldson, 2004).
The bomb calorimeter (IP 12/63 T) was used to determine the
gross calorific value (GCV) of pyrolysis oil.

3. Results and discussion

3.1. Catalyst characterization

3.1.1. SEM-EDX analysis

Surface morphology of the treated (calcined) and untreated fly
ash samples are shown in Fig. 4. It is evident that most of the par-
ticles were spherical in shape with high porosity. The fly ash con-
Fig. 3. Catalyst bed (a) top view and (b) side view.
sists of spherical, vitreous particles of different sizes. These

Fig. 4. SEM images of FA synthesized catalyst (a) fly ash in natural form (FAN), (b) fly ash calcined at 600 °C (FA-600), (c) fly ash calcined at 700 °C (FA-700), (d) fly ash
calcined at 800 °C (FA-800) and (e) fly ash calcined at 900 °C (FA-900).
 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130 119

Fig. 4 (continued)

particles are usually porous in nature and some pores may contain formed by the heavy metal ions when calcined at high tempera-
other smaller particles in their interior. The surface texture of fly tures (Musapatika et al., 2010).
ash particles appears to be smooth and also some vitreous, SEM-EDX analyses show that the particles of fly ash calcined at
unshaped fragments or quartz particles can be seen. The average 900 °C (Fig. 4e), contain large pore diameter compared to the fly
size of these particles is in the range of 0.1023 to 3.61 mm. SEM ash particles calcined between 600 °C and 800 °C. The surface con-
and EDX analysis of FA particles were performed to determine centration of (Si/Al) also gets decreased for the calcination temper-
the ratio of silicon (Si) and aluminium (Al) in these samples. Silica ature of 900 °C, due to the availability of low surface area. The
(Si) to Alumina (Al) ratio in these samples are significantly maximum (Si/Al) ratio was obtained at the calcination temperature
increased from 3.32 to 16.03 i.e., 3.32 for FA-600, 5.22 for FA-700 of 800 °C due to the availability of large surface area (310 m2/g)
and 16.03 for FA-800, when they were treated at different temper- (Table 4). It implies that calcination temperature plays an impor-
atures ranging from 600 °C to 800 °C. However, calcined fly ash at tant role to achieve maximum surface area with a maximum sur-
900 °C (FA-900) gives Si/Al ration of 1.43 (Table 4). This may be due face concentration of active component silica (Si) and alumina (Al).
to degradation of FA particles, micropores get collapse at such very
high temperature, resulting in very low surface area of 5.78 m2/g 3.1.2. BET analysis and pore size distribution
(Table 4) and low surface concentration of (Si/A) (Fig. 4e). Whereas, Table 4 shows that surface area and pore volume both increases
untreated fly ash gives Si/Al ratio of 2.18 due to the low surface with the increase in calcination temperature from 600 °C to 800 °C.
area, lesser amount of micropores and very high impurities get Whereas, further increase in temperature to 900 °C, surface area
deposited on the surface of the FA particles. The morphological gets reduced. The uncalcined or fresh fly ash (FAN) exhibit surface
changes in the fly ash during calcination process at the tempera- area of 1.74 m2/g and pore volume of 2.25 mL/g. The maximum
ture range of 600 °C to 900 °C is clearly noticed in the Fig. 4a-e. surface area of 310.40 m2/g is obtained when the fly ash is calcined
The spheres of fly ash were covered by precipitates and complexes at a temperature of 800 °C (FA-800). However, catalyst surface area
120 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130

Fig. 4 (continued)

decreased to 5.78 m2/g when calcination temperature is raised to and asymmetric stretching vibrations of the SiAOASi linkages of
900 °C. The increase in temperature upto 800 °C, raised the surface the zeolite framework. The vibration modes between 700 and
area 177.4 times (310.40 m2/g). It may be due to increase in tem- 580 cm1 are assigned to the internal vibration of SiO4 and AlO4
perature, the micropores get opened up which increases pore vol- tetrahedra symmetric stretching vibration. The H–OH bending
ume and surface area both upto heating of 800 °C. Beyond the vibrations of the adsorbed water molecules are observed between
calcination temperature (800 °C), the wall of micropores get col- 1700 and 1400 cm1. The IR spectroscopy carefully observes the
lapsed resulting in low surface area. Thus, the study on catalytic acidic hydroxyl OH groups of solid catalysts. The IR band at
pyrolysis of polyethylene using the catalyst FA-800 shows excel- 3700–3300 cm1 is a characteristic of protonated form of zeolite
lent performance in term of quantity and quality of liquid yield and its intensity is correlated with framework aluminium (FAL).
with higher BTEX production. The IR band at 3619 cm1 corresponds to bridging hydroxyl groups
of the Bronsted acid sites that are found responsible for catalyzing
3.1.3. FTIR of fly ash synthesized catalyst cracking.
Fourier Transform Infrared spectroscopy (FTIR) is an important Formation of silico aluminate crystalline material in FA-800 was
analysis technique which detects various characteristic functional confirmed by the shift of the band from 1102.3 cm1 for FA to
groups present in the synthesized catalyst. In order to collect sys- 979.87 cm1 for FA-800 on Fourier transform infrared (FTIR) spec-
tematic information about the chemical composition of the fly ash, tra (Fig. 5 and Table 5). An increase in tetrahedral Al (formation of
the resultant catalysts were examined using FTIR in the wave- zeolitic phases) would induce a shift of the band within the range
length range of 500–4000 cm1. Fig. 5 shows the FTIR spectra of of 1180–950 cm1 (which is assigned to the asymmetric internal T-
fly ash catalyst obtained at different calcination temperatures. O stretching vibration mode of the TO4tetrahedra, where T = Si or
The sharp peak at 450 cm1 and also the bands at 545 cm1, Al) to a lower wave number (Agarwal and Rani, 2017; Xie et al.,
585 cm1, and 600 cm1 could be assigned to the structurally sen- 2012). The four bands at 577, 612, 687 and 789 cm1 confirm the
sitive double five-member ring tetrahedral vibrations, and it is typ- formation of zeolitic material on synthesized fly ash catalyst
ical for the crystalline ZSM-5 zeolite. The characteristic bands (Sougazeh and Buhl, 2014). The FTIR absorption bands at 2856
between 850 and 1250 cm1 can be assigned to the symmetric and 2926 cm1, which are attributed to the symmetric and asym-
 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130 121

Fig. 4 (continued)

metric stretching vibrations of C-H of FA-800, and it indicates that interaction of smaller hydrocarbon molecules with FA catalyst in
FA-800 formed a bilayer micelle, rather than monolayer coverage vapor phase resulting in more aromatics in comparison to thermal
(Kung and Hayes, 1993). pyrolysis and A-type/liquid phase reactor arrangement.
It is seen in the Fig. 6a–c that liquid yield increases and solid
3.2. Product yield of pyrolysis process residue decreases with the increase in temperature for the thermal
pyrolysis. The maximum liquid yield of 68.02 wt% obtained at a
3.2.1. Effect of temperature temperature of 700 °C for the thermal pyrolysis. However, at a
Thermal and catalytic pyrolysis experiments (A-type and B- temperature of 800 °C, the obtained liquid yield was waxy at room
type) both were carried out at the temperature of 500 °C, 600 °C, temperature. The solid residue was decreased from 20 wt% to 7.5
700 °C and 800 °C, respectively. The catalytic pyrolysis was per- wt%, when temperature was increased from 500 °C to 800 °C. It
formed using green catalyst fly ash in natural form (FAN), fly ash implies that more decomposition of higher molecular weight solid
calcined at 600 °C (FA-600), fly ash calcined at 700 °C (FA-700), residue takes place at high temperature resulting in more liquid
fly ash calcined at 800 °C (FA-800), fly ash calcined at 900 °C (FA- yield and non-condensable gases. Similarly, catalytic pyrolysis at
900). The product yields obtained by the thermal and catalytic a maximum temperature of 800 °C produced waxy liquid yield
pyrolysis were compared to show the improvement in product, irrespective of reactor arrangement (A-type and B-type/
qualitatively and quantitatively for the liquid yield, gaseous yield multiphase) and catalyst used (FAN, FA-600, FA-700, FA-800 and
and solid residue, respectively (Fig. 6a–d). As already mentioned FA-900).
‘‘A” refers to the catalytic pyrolysis of polyethylene in liquid phase The catalytic pyrolysis at a temperature of 700 °C on FA-800
only and ‘‘B” refers to both liquid and vapor phase/multiphase cat- catalyst resulting in maximum liquid yield of 78 wt% for A-type
alytic pyrolysis of PE. In the A-type reactor arrangement melted and 73.12 wt% for B-type/multiphase reactor arrangement, respec-
liquid PE interacts with FA catalyst particles and leaving relatively tively. Although, at the same temperature catalyst FA-900 pro-
smaller hydrocarbon molecules. Whereas, B-type/multiphase reac- duced liquid yield of 80.02 wt% which is waxy at room
tor arrangement provides opportunities for catalyst and PE interac- temperature. It may be due to poor quality of catalyst with very
tion in the bottom of the reactor (liquid phase) followed by low surface area (5.78 m2/g) of FA-900 as shown in Table 4. Use
122 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130

Fig. 4 (continued)

Table 4 It is also seen in the Figs. 6a–d and 7 that the catalyst FA-800
Surface area, pore volume and (Si/Al) ratio of FA catalyst.
produced maximum liquid yield for A-type (liquid phase) than
Name of catalysts Surface area (m2/g) Pore volume (ml/g) (Si/Al) ratio the B-type/multiphase irrespective of pyrolysis temperature used.
FAN 1.74 2.25 2.18 However, the gaseous yield for B-type/multiphase was always high
FA-600 10.98 14.19 3.32 for all temperatures in comparison to A-type. The solid residue is
FA-700 25.95 19.34 5.22 also very low for B-type reactor arrangement. It may be due to
FA-800 310.40 43.95 16.03
the presence of catalyst in both phases (B-type/liquid and vapor
FA-900 5.78 59.28 1.43
phase) the higher hydrocarbon molecules which are produced at
the bottom of the reactor (liquid phase) will move through the
vapor phase catalyst bed, which helps in further selective cracking
of catalyst FA-800 reduced the solid residue and improved the liq-
of the higher hydrocarbon molecule to lower aromatic and gaseous
uid yield quantitatively and qualitatively in terms of aromatics
range hydrocarbon. Thus, the aromatic content, mainly BTEX was
BTEX at 700 °C. The gaseous yield also increased dramatically for
found to be the highest amount for B-type/multiphase reactor
FA-800 catalyst in B-type/multiphase arrangement at the same
arrangement in comparison to catalytic pyrolysis A-type reactor
temperature. The catalyst affects the pyrolysis mechanism and
arrangement and thermal pyrolysis.
converts the heteroatoms into gaseous range hydrocarbons. The
The catalyst FA-800 produces maximum amount of gaseous
reaction takes place in a recognized pyrolysis process of polyethy-
yield of 25.2 wt% at a temperature of 700 °C for the B-type/
lene [(C2H4)nH2] can be expressed as (Eq. (5)):
multiphase pyrolysis of PE in comparison to liquid phase
(A-type) arrangement among all types of catalyst used (Fig. 6c).
ðC2 H4 Þn  H2 þ Q ! Liquid hydrocarbon þ Gas hydrocarbon The FA-800 affects the pyrolysis mechanism and converts heteroa-
þ Solid residue ð5Þ toms into gaseous hydrocarbons. As BET surface area analysis and
SEM-EDX suggest that FA-800 catalyst could be the superior cata-
where Q is the heat that needs to be input to the reactor for the lyst due to its maximum surface area 310.10 m2/g and (Si/Al) ratio
reactions to take place (Gaurh and Pramanik, 2018). of 16.03. Thus, probably the use of FA-800 resulting in slightly low
 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130 123

Fig. 5. FT-IR spectrometry of synthesized fly ash catalyst; FAN, FA-600, FA-700, FA-800 and FA-900.

Table 5
Comparison and shifting of bands data for FAN, FA-600, FA-700, FA-800 and FA-900 in FTIR spectroscopy.

Wave number (cm1) Possible assignment Observed value (cm1)

FAN FA-600 FA-700 FA-800 FA-900
3700–3300 Stretching vibration of AOH group and Silanol (Si-OH) 3767.8 3757.2 3746.8 3722.9 3736.3
3646.3 3605.3 – 3619.1 –
1700–1400 AOH deformation & bending vibration of interstitial water 1668.2 1659.8 1652.1 1644.5 1646.2
1250–850 Asymmetric stretching of internal tetrachedral TO4, SiAOASi (T = Si, Al) 1102.3 1086.2 1035.3 979.87 984.35
700–580 Symmetric stretching of internal tetrachedral TO4 (T = Si, Al) – – – 668.2 –
600 584.8 578.4 576.2 577.3

quantity of liquid yield but improved the quality of liquid oil in always higher for B-type/multiphase pyrolysis at this temperature
terms of aromatics BTEX. It is important to note that FA-900 cata- range. It implies that the A-type/liquid phase (single stage) only
lyst gives highest amount of liquid yield of 80.02 wt% at 700 °C. converts waste polyethylene to liquid range hydrocarbons due to
However, the liquid yield is highly waxy at room temperature with its shorter duration of interaction between cracked hydrocarbons
a lower content of BTEX. and FA-800 catalyst particles. However, B-type/multiphase pyroly-
Fig. 7 shows the comparison between liquid, gaseous and solid sis converts the cracked liquid range hydrocarbons to lighter hydro-
yield for A-type and B-type reactor arrangements at different tem- carbon molecules in two stages when hydrocarbon vapors from the
peratures using FA-800 catalyst. It is seen in the Fig. 7 that the liquid bottom of the reactor/liquid escape and pass through the catalyst
yield is always high for the temperature ranging from 500 °C to 800 bed in the vapor phase (Fig. 2c). In addition, multiphase (B-type)
°C for A-type reactor arrangement. However, gaseous yield is gives more aromatics BTEX in comparison to A-type.
124 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130

3.2.2. Effect of calcination temperature of FA catalyst ment, respectively. It is clear from this observation that B-type/
Table 6 shows the effect of calcination temperature of fly ash cat- multiphase produced more gaseous yield than A-type/liquid phase
alyst on the product yield obtained via pyrolysis of polyethylene at a pyrolysis and thus liquid yield is less for B-type/multiphase. It
pyrolysis temperature of 700 °C. As the pyrolysis temperature of may be due to two stage catalytic pyrolysis in B-type arrangement,
700 °C resulting in better quality of liquid yield with appreciable the further selective cracking at vapor phase of comparatively
amount of liquid and gaseous hydrocarbon, effect of calcination lighter hydrocarbons molecules which are formed by the catalytic
temperatures on product yields are presented in Table 6 for this cracking at the bottom of the reactor (Fig. 2c). Lopez et al. 2012
temperature only. It is seen from the Table 6 that the liquid yield reported that the use of catalyst improves the quality of liquid yield
increases with the increase in calcination temperature up to 800 via aromatization when Si-Al based catalyst is used. The solid resi-
°C. Beyond this calcination temperature, the catalyst FA-900 gives due was also found very low for FA-800 catalyst in comparison to
liquid yield of 80.02 wt% which is highly waxy in nature. Moreover, other catalyst and it was too low (1.66 wt%) for B-type/multiphase
the liquid yield is always high for the catalytic pyrolysis and maxi- pyrolysis than that of A-type/liquid phase (1.76 wt%) due to the
mum amount of good quality liquid yield of 78.2 wt% is obtained for effective and selective two stages catalytic cracking for B-type reac-
A-type/liquid phase catalytic pyrolysis using FA-800 (calcined at tor arrangement. Gaurh and Pramanik, 2018 investigated on the
800 °C) catalyst at 700 °C. However, same catalyst FA-800 produced multiphase catalytic pyrolysis of plastic waste polyethylene (PE)
liquid yield of 73.12 wt% for B-type/multiphase catalytic pyrolysis using ZSM-5 in three different phases within the reactor batch by
at this temperature. Moreover, the gaseous yield of 25.22 wt% and batch systematically, keeping the catalyst in A type-vapor phase,
20.04 wt% were obtained for B-type and A-type reactor arrange- B type- liquid phase and C type- vapor and liquid phase (multi-

% Liquid
% Gas
80 % Solid
70

60

50

40
% yield

30

20

10

0
A B A B A B A B A B
Thermal FAN FA-600 FA-700 FA-800 FA-900

(a)

% Liquid
90
% Gas
80 % Solid

70

60

50
% yield

40

30

20

10

0
A B A B A B A B A B
Thermal FAN FA-600 FA-700 FA-800 FA-900

(b)
Fig. 6. Comparison between liquid, gaseous and solid residue obtained by the thermal and catalytic pyrolysis of PE at (a) 500 °C, (b) 600 °C, (c) 700 °C and (d) 800 °C.
 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130 125

% Liquid
90 % Gas
% Solid
80
70
60
50
% yield

40
30
20
10
0
A B A B A B A B A B
Thermal FAN FA-600 FA-700 FA-800 FA-900

(c)

% Liquid
90
% Gas
80 % Solid

70
60
50
40
% yield

30
20
10
0
A B A B A B A B A B
Thermal FAN FA-600 FA-700 FA-800 FA-900

(d)
Fig. 6 (continued)

100
from B-type (liquid phase) reactor arrangement at a temperature of
700 °C. Whereas, C-type (multiphase/vapor and liquid phase) pro-
90 duced maximum liquid yield of 46.36 wt%, gaseous yield of 49.46
80 wt% and solid residue of 4.18 wt%. The analyzes of product yields
show that synthesized FA-800 catalyst is equally efficient as that
70
Liquid (A-type) of commercial ZSM-5.
60 Gas (A-Type) GC-FID analysis of the liquid yield shows the highest amount of
Solid (A-type) aromatics BTEX for FA-800 catalyst at a pyrolysis temperature of
% Yield

50
Liquid (B-type) 700 °C in B-type reactor arrangement. Thermal pyrolysis at the
40 Gas (B-type) same temperature (700 °C) produced lowest amount of liquid yield
Solid (B-type) (68.02 wt%), gaseous yield (16.02 wt%) and highest amount of solid
30
residue (15.16 wt%).
20 As discussed earlier, calcination temperature plays a crucial role
10 during the synthesis of FA catalyst resulting in the formation of
superior quality FA-800 catalyst at a calcination temperature of
0 800 °C. Thus, the FA-800 catalyst could effectively convert waste
500 600 700 800
polyethylene to valuable aromatics BTEX with better quality of liq-
Temperature (oC)
uid and gaseous yield at a pyrolysis temperature of 700 °C.
Fig. 7. Comparison of liquid, gas and solid yield for reactor arrangements A-type
and B-type using catalyst FA-800. 3.2.3. Effect of reaction time on conversion rate
The effect of reaction time on the conversion rate for thermal
phase), respectively. The maximum liquid yield of 58.68 wt%, gas- and catalytic pyrolysis of polyethylene at a temperature of 700 °C
eous yield of 36.56 wt% and solid residue of 4.76 wt% were obtained is shown in Fig. 8. The conversion rate decreases with the increase
126 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130

Table 6
Product yield of pyrolysis using polyethylene at 700 °C.

Pyrolysis type Liquid (Wt %) Gas (Wt %) Solid (Wt %)

Thermal 68.02 16.82 15.16
Catalytic using FAN A-type 68.20 18.6 13.2
B-type 71.70 15.9 12.4
Catalytic using FA-600 A-type 70.24 18.4 11.36
B-type 76.14 13.96 9.90
Catalytic using FA-700 A-type 71.36 17.78 10.86
B-type 70.96 21.88 7.16
Catalytic using FA-800 A-type 78.20 20.04 1.76
B-type 73.12 25.22 1.66
Catalytic using FA-900 A-type 80.02 (waxy) 18.88 1.10
B-type 76.22 (waxy) 23.10 0.68

100 time range 1–7 min and 18–20 min GC peaks are matched for ther-
90 mal pyrolysis and diesel oil only. It may be due to the presence of
compounds of similar boiling point range.
80 Fig. 10 shows the calibration characteristics to measure mainly
70 benzene, toluene, ethyl benzene and xylene (BTEX) as a function of
their % peak area under the curve. High purity HPLC grade benzene,
60
% Conversion

toluene, ethyl benzene and xylene were procured from Fisher Sci-
50 Liquid (Thermal) entific, India to get the calibration characteristics. Benzene,
40 Liquid (Catalytic) toluene, ethyl benzene and xylene (BTEX) were mixed in different
Solid residue (Thermal) ratios to get a mixture of known composition and their GC data (%
30 Solid residue (Catalytic) area) for the same. GC-FID of these mixtures were performed for
20 the calibration characteristics of benzene, toluene, ethyl benzene
and xylene as shown in Fig. 10. The amount (wt. %) of benzene,
10
toluene, ethyl benzene and xylene in the liquid yield obtained
0 via thermal and catalytic pyrolysis, were measured using these cal-
0 5 10 15 20 25 30 35 40
ibration characteristics.
Time (min) From Table 7, it is seen that wt. % of aromatic content in thermal
Fig. 8. Time vs. conversion rate of liquid and solid residue for thermal and catalytic
pyrolysis of polyethylene was around 10.91 wt%. Whereas, it is
pyrolysis at 700 °C. higher in the case of catalytic pyrolysis (A-type and B-type). The
maximum/highest amount of aromatic content i.e., BTEX was
found for the catalyst FA-800. It may be due to the very high sur-
face area 310.40 m2/g of FA-800 catalyst, high Si to Al ratio
in reaction time. This indicates that the reaction time plays vital (=16.03) could provide more acidic sites with higher selectivity
role for the conversion of PE and achieving product yield. After which produces maximum amount of more aromatics (BTEX).
25 min, the conversion rate becomes constant for both thermal Moreover, vapor-liquid phase/multiphase (B-type) produced more
and catalytic pyrolysis. The Fig. 8 shows that there is no conversion BTEX (22.10 wt%) than that of liquid phase (A-type) catalytic pyrol-
after 25 min of reaction time. Thus, to ensure complete conversion ysis (21.33 wt%). For the B-type pyrolysis, smaller hydrocarbon
and achieve maximum product yield, both thermal and catalytic molecules are formed due to catalytic pyrolysis of PE at the liquid
pyrolysis were performed for 30 min. phase followed by the second stage selective catalytic cracking of
liquid range hydrocarbon molecules on FA-800 catalyst in the
3.3. Pyrolysis products analyses vapor phase (Fig. 2c). As per the proposed reaction schemes in
the published literature, B-type/multiphase pyrolysis gives maxi-
3.3.1. Gas chromatography mum BTEX of 22.10 wt% which is shown in Fig. 11 (Gaurh and
Fig. 9a–c shows the GC-FID of the commercial kerosene oil, die- Pramanik, 2018). However, the reactor arrangement A-type allows
sel oil and pyrolysis oil derived by the thermal and catalytic pyrol- PE to go through catalytic pyrolysis in a single stage i.e., liquid
ysis (A-type and B-type) of the waste polyethylene at 700 °C. The phase only. Thus, catalytic pyrolysis A-type gives lower BTEX than
catalyst used was FA-800 for catalytic pyrolysis. The important that of B-type/multiphase. It is generally proposed that on acid cat-
and prominent peaks obtained at same retention time for the alysts the aromatization of alkanes occurs through protolysis of
pyrolysis oil (700 °C), commercial kerosene oil and diesel oil are alkane, cracking of carbonium ion to alkane and alkene, oligomer-
grouped. The chromatograms for pyrolysis oil (700 °C) are very ization of alkenes, cyclization of oligomerized products and forma-
close to kerosene and diesel oil in the retention time range tion or aromatics from cyclic rings by hydrogen transfer (Fig. 11).
between 7 and 18 min for thermal pyrolysis and in between 5 Two important outcomes of this innovative and unique research
and 18 min for A-type and B-type catalytic pyrolysis. This range are (i) B-type/multiphase catalytic process gives always maximum
may be specifically interesting for the pyrolysis oil (700 °C) which amount of benzene, toluene, ethyl benzene and xylene (BTEX) in
consist of compounds, are similar as that of kerosene oil and diesel comparison to any other processes, as it is in-situ two stages cat-
oil in terms of chemical structure of compounds and composition alytic pyrolysis and (ii) laboratory synthesized FA-800 catalyst is
(Nicholas, 1998). Moreover, it is seen in Fig. 9b and c that maxi- of superior quality in comparison to FA-500, FA-600, FA-700 and
mum numbers of peaks of A-type and B-type pyrolysis oil are FA-900 catalyst as it gives all time highest amount of BTEX yield
matched with diesel and kerosene. However, within the retention (22.10 wt%).
 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130 127

Fig. 9. Gas chromatography characteristic of diesel oil (commercial), kerosene oil (commercial) and pyrolysis oil obtained from the polyethylene at a temperature of 700 °C
using (a) thermal pyrolysis, (b) catalyst in liquid phase (A) and (c) catalyst in both liquid and vapor phase (B).

Thus, B-type/multiphase catalytic pyrolysis on FA-800 can be cause any trouble in most of the engines. Liquid fuel obtained by
recommended as a suitable process design to convert waste poly- catalytic pyrolysis (B-type) of waste PE gives GCV of 11,786 Cal/g
ethylene into BTEX which is value added upgraded product. It is which is in the range of gasoline and diesel and thus, it could per-
seen in Table 7 that commercial gasoline also contains about form relatively well in IC engines. The carbon residue is also <1 wt%
31.2 wt% BTEX to improve octane rating of fuel. However, it is pro- irrespective of types of pyrolysis process performed except for the
posed that benzene should be removed before the pyrolysis oil/liq- FA-900 catalyst. As already mentioned that FA-900 catalyst gives
uid yield (B-type) is used as an alternative fuel. Moreover, liquid yield which is waxy at room temperature. The waxy liquid
recovered benzene could also be used as raw material for many yield might contain high molecular weight aromatics which gives
chemicals manufacturing. maximum carbon residue of 1.6 wt% when tested by the Rams bot-
tom carbon residue method.
3.3.2. Physicochemical properties of pyrolysis oil It should be noted that lower aromatics/BTEX do not give car-
Table 8 shows the physicochemical properties of liquid fuel bon residue. From the result, it is seen that these could be possible
obtained by thermal and catalytic pyrolysis of waste PE at opti- feedstock for further upgrading to use in diesel engine besides
mum process condition. The appearance of the oil is dark yellowish recovery of BTEX as a valuable product from the pyrolysis of PE.
free from visible sediments. The flash point of the liquid product is Low flash point indicates that it could be used in IC engine during
in the comparable range with gasoline and diesel which will not winter or cold climate region effectively.
128 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130

Fig. 9 (continued)

80 Benzene 4. Conclusions
Toluene
Xylene
70 The in-situ pyrolysis and aromatization of plastic waste PE on
Ethyl Benzene
Linear (Benzene) synthesized FA catalyst using two different types of catalyst
60 Linear (Toluene) arrangements (A-type and B-type) was studied for the first time
Linear (Xylene) and was not reported before in the available literature. The opti-
50 Linear (Ethyl Benzene) mum calcination temperature of fly ash for catalyst synthesis
was 800 °C, as FA-800 catalyst showed excellent performance for
40 aromatization of pyrolysis product in the reactor. The maximum
% Area

surface area and (Si/Al) ratio of FA-800 catalyst were 310 m2/g
30 and 16.03, respectively.
The experimental results on catalytic pyrolysis of PE and analy-
20 ses of products show that the developed process could be a very
good option for production of mainly aromatics BTEX. B-type/
10 multiphase catalytic pyrolysis on FA-800 catalyst at a temperature
of 700 °C resulted in the highest amount of aromatics/BTEX of
0 22.10 wt% with respect to any other process and catalysts tested
0 20 40 60 80 in this study. The flash point and fire point of pyrolysis oil were
Yield (wt. %) found to be in the range of kerosene irrespective of pyrolysis pro-
cess used. Lower amount of carbon residue of pyrolysis oil of about
Fig. 10. Calibration characteristics for benzene, toluene, ethyl benzene and xylene.

Table 7
The aromatic content (BTEX) in pyrolysis oil obtained at 700 °C on various types of catalyst.

Sources of oil Benzene (wt. %) Toluene (wt. %) Ethyl Benzene (wt. %) Xylene (wt. %) Total (wt. %)
Thermal pyrolysis 0.0024 0.3211 4.3750 6.2189 10.9173
Catalytic (FAN) A-type 0.0863 6.5512 4.8601 1.1329 12.6305
B-type 0.1122 6.0047 4.9849 1.2008 12.3025
Catalytic (FA-600) A-type 0.0439 6.2145 5.1100 1.2543 12.6227
B-type 0.1856 5.8440 4.0399 0.8128 10.8826
Catalytic (FA-700) A-type 0.0683 6.4640 4.5616 0.9765 12.0700
B-type 3.0527 6.1364 4.4048 0.8596 14.4536
Catalytic (FA-800) A-type 5.7787 7.8666 5.5266 2.1645 21.3364
B-type 6.3643 7.9536 5.5694 2.2215 22.1089
Catalytic (FA-900) A-type 0.4435 5.6971 3.9613 0.7676 10.8696
B-type 0.0853 4.8419 3.7316 0.6187 9.2774
Commercial diesel 0.1485 0.5416 4.3789 4.2623 9.3311
Commercial kerosene 0.0144 0.0008 2.0591 2.0043 4.0786
Commercial gasoline 0.8829 14.8767 5.2607 15.4282 36.4487
 P. Gaurh, H. Pramanik / Waste Management 77 (2018) 114–130 129

Fig. 11. Reaction scheme of aromatization.

Table 8
hysicochemical properties of pyrolysis oil/fuel obtained by thermal and catalytic pyrolysis of waste PE at optimized condition (700 °C).

Physicochemical Properties Test method Results obtained

Thermal Pyrolysis Catalytic Pyrolysis
FAN FA-600 FA-700 FA-800 FA-900
Flash point (°C) ASTM D 92 27 27 27 27 26 28
Fire point (°C) ASTM D 92 32 33 33 32 31 33
Carbon residue (wt.%) IP 14/65 0.28 0.52 0.45 0.41 0.38 1.62
Specific gravity ASTM D 1298 0.768 0.759 0.754 0.748 0.731 0.769
API gravity (°) API correlation 52.65 54.93 56.17 57.67 62.07 52.50
Calorific value (Cal/g) IP 12/63 T 10,982 11,037 11,196 11,238 11,786 8914

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