Process Safety and Environmental Protection 146 (2021) 383–395

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

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

Production of diesel range hydrocarbons from crude oil sludge via

microwave-assisted pyrolysis and catalytic upgradation
P. Francis Prashanth a , Burada Shravani a , R. Vinu a,∗ , M. Lavanya b , V. Ramesh Prabu b
a
Department of Chemical Engineering and National Center for Combustion Research and Development, Indian Institute of Technology, Madras, Chennai,
600036, India
b
Chennai Petroleum Corporation Limited (CPCL), Manali, Chennai, 600068, India

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

Article history: Crude oil sludge is one of the key waste streams of the refinery, and it contains valuable hydrocarbons that
Received 14 May 2020 can be potentially converted to fuels and petrochemicals. This study is unique in evaluating the effects
Received in revised form 21 July 2020 of activated carbon susceptor (ACS) and catalysts to selectively recover hydrocarbons from crude sludge
Accepted 18 August 2020
via microwave-assisted pyrolysis (MAP). Two different sludge samples received from the refinery, viz.,
Available online 25 August 2020
sludge from storage tank bottoms (sludge 1) and mixed sludge (sludge 2), were characterized. Sludge
1 was rich in volatile matter and hydrocarbons, while sludge 2 contained a significant amount of ash,
Keywords:
nitrogen, sulfur and iron. At 600 W microwave power with 10 % ACS loading, maximum oil yield of 87.3
Crude oil sludge
Activated carbon
wt.% was obtained from sludge 1, while it was 41.2 wt.% from sludge 2. An increase in yield of gaseous
Susceptor products with a concomitant decrease in oil yield was observed when the sample heating rates were
Microwave pyrolysis increased by using high microwave power or high loading of ACS. MAP of crude sludge at 600 W with
Catalytic upgradation 10 % ACS produced char and oil with higher heating values (HHV) of 26 and 42.4 MJ kg−1 , respectively.
H-ZSM-5 For the first time, ex situ catalytic upgradation with H-ZSM-5 and regenerated fluid catalytic cracking
Hydrocarbons (FCC) catalyst was employed to produce refinery blendstocks from crude sludge through MAP. Catalytic
upgradation resulted in significant deoxygenation of pyrolysates with low oxygen content (<5%), and high
carbon (80−85 wt.%) and hydrogen (12−14 wt.%) content in the oil fraction. The HHV of the upgraded oil
was 44−45 MJ kg−1 . Importantly, the selectivity to hydrocarbons in the diesel range (C8 to C20) increased
by more than 10 % in the oil fraction containing paraffins, iso-paraffins, and aromatic hydrocarbons. This
study proves that a liquid fuel, resembling refinery blendstock, can be generated from crude oil sludge
by adopting this process.
© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Crude oil sludge or crude sludge is an undesirable by-product
of the petroleum refining industry. It is formed during storage and
transportation operations when the heavy fractions separate from
the crude oil and settle at the bottom of storage vessels. Its high
viscosity is attributed to the presence of long-chain paraffins and
iso-paraffins, which bond together over time as a result of induced
dipole forces (Bell, 2015). The properties of the crude sludge can
be very different from that of the parent crude. Notably, crude
sludge contains a high amount of sediments, moisture, and paraf-
fins. The composition of the sludge also varies based on its source.
∗ Corresponding author.
E-mail addresses: prashanth.francis7@gmail.com (P. Francis Prashanth),
shravanireddy73@gmail.com (B. Shravani), vinu@iitm.ac.in (R. Vinu),
lavanya@cpcl.co.in (L. M.), rameshprabu@cpcl.co.in (V. Ramesh Prabu).
For example, sludge from crude oil tank bottom contains a lower
amount of ash (2–4 %) compared to that generated from a wastewa-
ter treatment plant in the refinery, which contains high amounts of
sediments (32 %) and moisture (26 %) (Shie et al., 2000; Chen, 2016;
Hu et al., 2017; Karayildirim et al., 2006). Surveys have shown that
processing 500 tons of crude oil produces one ton of oily sludge
(Islam, 2015). With a combined annual refining capacity of 252 mil-
lion metric tons, Indian refineries generate a total of approximately
500,000 tons of sludge per year (Central Statistics Office, 2019).
Crude sludge is separated during storage tank maintenance
operation. The accumulation of sludge in tanks causes gauging
problems, inaccuracies in crude composition, uncertainties in avail-
able volume, and lowering of the storage capacity of the tank. The
removal of sludge from the tank bottom is a costly, time consum-
ing, and labor-intensive process. Hence, there is a need to recover
the lost expenses through the extraction of useful products from
the sludge. From an environmental perspective, crude sludge has

https://doi.org/10.1016/j.psep.2020.08.025
0957-5820/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
384 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395
been classified as a hazardous waste by many countries, and uncon-
trolled disposal of crude sludge can be deteriorative to humans and
the eco-system (Bhattacharyya and Shekdar, 2003). The reviews by
Islam (2015) and Johnson and Affam (2019) show that oil recov-
ery from petroleum sludge can be achieved by solvent extraction,
centrifugation, using surfactants, pyrolysis, electrokinetic method,
ultrasonic irradiation, and froth flotation. However, the lack of
versatility of these methods to treat sludges with wide-ranging
properties concerning sediments, moisture content and chemical
composition leads to major issues in their implementation. Incin-
eration, bio-remediation, and landfilling are the available disposal
methods of the residue generated after oil extraction from crude
sludge. More importantly, the adoption of any of these processes
by the refinery requires maximum recovery of hydrocarbons in
the liquid phase, and condensed ring aromatic carbons and metal
species in the solid residue. Moreover, the release of toxic metals
and other gaseous species in the environment should be contained
while adopting any of these strategies.
Compared to conventional heating, the use of microwaves to
accelerate the heating rate of the sample and reduce the processing
time with reasonable energy recovery has attracted the attention
of researchers worldwide (Motasemi and Afzal, 2013). Microwave-
assisted pyrolysis (MAP) of a variety of complex feedstocks like
coal, lignocellulosic biomass, plastics, waste tire, sewage sludge
and lignin to produce fuel molecules, energy and chemicals have
been carried out by a number of researchers (Reddy and Vinu,
2018; Yerrayya et al., 2018; Zhang et al., 2020). Feedstocks that
contain a high amount of moisture, fixed carbon and ash are likely
to experience better heating rates due to their superior microwave
absorbing capacity. Lam and Chase (2012) compared conventional
electric heating with microwave-assisted heating for the pyroly-
sis of waste oils. They observed that MAP facilitated the cracking
of heavier hydrocarbons to the C5-C18 range. The generation of
localized hot-spots plays a major role in differentiating the liquid
product composition from conventional and microwave pyroly-
sis. These high-temperature zones generated during MAP increase
the severity of cracking of long-chain aliphatic compounds and
polyaromatic hydrocarbons (PAHs) to form low molecular weight
condensates and gases. Domínguez et al. (2006) compared the
influence of conventional and microwave heating mechanism on
the products from pyrolysis of sewage sludge. They showed that oils
produced from MAP with char as a microwave absorber produced
a lower toxicological effect by reducing the amount of PAHs (5%)
compared to that produced by using an electrically heated furnace
(80 %).
Studies on the pyrolysis of oil-based feedstocks have been
successful in demonstrating the role of additives, catalysts and
operating conditions to improve the physicochemical properties
of the oil, and improve the value of gaseous products. Lam and co-
workers (Lam et al., 2010, 2012; Mahari et al., 2016) carried out
extensive research to determine the effects of reaction conditions
like temperature, heating rate, carrier gas flow, and catalyst load-
ing in microwave pyrolysis of automotive and shipping oils. The
resultant oils possessed excellent heating values (∼45 MJ kg−1 ) and
distillation characteristics similar to gasoline with low amounts of
PAHs, oxygen, sulfur, and heavy metals. Similarly, Shie et al. (2004)
investigated the effect of additives like fly ash and zeolites in con-
ventional pyrolysis of oily sludge using thermogravimetric analysis,
and achieved maximum yield of gases (38 %) with the addition of 5%
fly ash. Huang et al. (2015) conducted two-stage fixed-bed pyrolysis
of oily sludge in an electrically heated quartz tube, and showed that
the gaseous product can be selectively upgraded in the presence of
dolomite to produce hydrogen-rich syngas.
The use of microwave absorbers or susceptors to accelerate
the microwave heating process is well documented in the litera-
ture (Chen, 2016; Reddy and Vinu, 2018; Suriapparao and Vinu,
2015; Wan et al., 2009; Yerrayya et al., 2018). Even though a
variety of materials like (a) carbonaceous materials (graphite, bio-
char and activated carbon), (b) metal oxides, carbides, acids and
salts (K2 Cr2 O7 , Al2 O3 , TiO2 , SiO2 beads, garnet, SiC, KAc, H3 BO3 ,
Na2 HPO4 , MgCl2 , AlCl3 , CoCl2 , and ZnCl2 ), and (c) wastes like fly
ash and cement wastes can be used as susceptors, it is also essential
that the susceptor should be cheap, sustainable, reusable, and easily
available/prepared. Based on these criteria, carbonaceous mate-
rials, especially activated carbon and pyrolysis char, are valuable
susceptors.
Catalytic upgradation of pyrolysis vapors is a key step to control
and tailor the carbon number range of the hydrocarbons produced
from the feedstocks. Padmaja et al. (2009) used fluid catalytic crack-
ing (FCC) catalyst and demonstrated its use to promote the cracking
of long-chain hydrocarbons present in the bio-crude derived from
Calotropis procera biomass. An aromatic-rich oil at 78 % yield was
produced, and the gaseous product comprised mainly of C3-C5
hydrocarbons. Xie et al. (2014) showed that H-ZSM-5 is a stable
catalyst at high temperatures, and facilitates the deoxygenation
of products from microwave-assisted catalytic pyrolysis of sewage
sludge. Tripathi et al. (2015) demonstrated the catalytic fast pyroly-
sis of oxidized engine oils using ZSM-5, Zeolite-Y (ZY), and Zeolite-␤
(Z␤) catalysts using an analytical micropyrolyzer. They showed that
the use of ZSM-5 catalyst resulted in the formation of alkenes and
cycloalkenes, while the use of ZY and Z␤ catalysts led to the for-
mation of alkanes. About 65 % of C6 to C15 hydrocarbons were
produced using ZY catalyst. Suriapparao et al. (2020) demonstrated
the production of light fuel oil from MAP of biomass-polymer mix-
tures by upgrading the pyrolysates over HZSM-5 catalyst. A clear
reduction in viscosity of the oil with a higher extent of deoxygena-
tion was achieved when the mass of catalyst in the upgradation
section was increased. Another study featuring HZSM-5 in the
upgradation of bio-oil from sawdust highlighted its deoxygenation
capability through a significant increase in the production of water,
whose yield doubled from 14 % in non-catalytic experiments to 28
% in catalytic experiments (Olazar et al., 2000). In a study by Jiang
et al. (2020), tandem microwave pyrolysis and a catalytic reform-
ing system were employed using ZSM-5/SiC catalyst to produce
hydrocarbon-rich bio-oil from soybean soapstock. The oxygenates
in bio-oil reduced significantly from 54 % in non-catalytic experi-
ments to 23 % after catalytic upgradation.
Wang et al. (2014) used H-ZSM-5 for both in situ and ex situ
pyrolysis of poplar biomass. In situ catalytic pyrolysis yielded a high
amount of PAHs, whereas ex situ catalytic upgradation promoted
the formation of olefins like propylene and ethylene, and monoaro-
matics like benzene, toluene and xylene (BTX). The pyrolysates
experience lower mass transfer rates in in situ catalysis, and are
in contact with the catalyst surface for longer time periods. How-
ever, in the case of ex situ catalytic pyrolysis, the quick desorption of
vapors limits the formation of PAHs. This was also reflected in high
coking of the in situ catalyst (31 %) compared to ex situ catalyst (19
%). Another study by Iisa et al. (2016) compared in situ and ex situ
catalysis of pine wood using H-ZSM-5 in a bubbling fluidized bed
reactor. They observed a relatively higher accumulation of metals
(Ca, Fe, Zn and K) from the ash of biomass on the catalyst in in situ
catalysis. This shows that faster deactivation of the catalyst occurs
in in situ catalytic pyrolysis.
Although a number of studies demonstrate in situ catalytic
pyrolysis and ex situ catalytic upgradation of pyrolysates from a
variety of feedstocks, there exists a void in the literature on the
valorization of crude sludge via pyrolysis coupled with catalytic
upgradation. To the best of our knowledge, this is the first study
to demonstrate the production of refinery blendstocks via catalytic
upgradation of pyrolysates from MAP of crude sludge. The objec-
tives of this study are three-fold. Firstly, to thoroughly characterize
two different types of crude sludge samples obtained from the
 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395
refinery, and select the best one for catalytic upgradation. Secondly,
to optimize the operating parameters like microwave power and
susceptor loading in order to achieve maximum recovery of pyrol-
ysis vapors for catalytic upgradation. Thirdly, to demonstrate the
production of diesel-range hydrocarbons using H-ZSM-5 and FCC
catalysts, and to thoroughly characterize all the products, viz., oil,
char, coke and gases, in order to understand the extent of valoriza-
tion of the feedstock and product quality.
2. Experimental section
2.1. Feedstock and product characterization
The two different crude oil sludge samples were provided by
Chennai Petroleum Corporation Limited (CPCL) located in Manali,
Chennai. The two sludge samples are henceforth denoted as ‘sludge
1’ and ‘sludge 2’. Sludge 1 was recovered from a crude oil stor-
age tank during a cleaning operation, while sludge 2 is a mixed
sludge sample that was already subjected to oil extraction by phys-
ical treatment of multiple sludges. A visual inspection of both the
sludge samples (Fig. 1) showed that sludge 1 had a toothpaste-like
consistency, while sludge 2 was similar to wet mud. The selection
of these two feedstocks highlighted a sharp contrast in the types
of sludges that are found in a refinery, and also demonstrates the
ability of MAP to process a wide range of sludges. Dichloromethane
(DCM, HPLC grade) was procured from Merck, India.
Thermogravimetric (TG) analysis was carried out in an SDT Q600
TG analyzer (T.A. Instruments, Waters GmbH, Austria) using N2
gas at 100 mL min−1 . The sample was heated from ambient to
985 ◦ C at 20 ◦ C min−1 to obtain the decomposition pattern of the
sludge samples. The metallic composition of the sludge samples
was determined using Inductively Coupled Plasma-Optical Emis-
sion Spectrometer (ICP-OES, Model: Perkin Elmer Optima 5300 DV
ICP-OES). Crude sludge samples were placed in a muffle furnace and
heated to 650 ◦ C at a heating rate of 10 ◦ C min−1 to burn out the
carbon in the samples and produce ash. The samples were weighed
in reaction vessels and digested using 8 mL hydrochloric acid and
2 mL nitric acid. After a reaction time of 1 min, the vessels were
sealed and then placed in the microwave, and heated to 170 ◦ C.
After digestion, the samples were diluted to 100 mL in volumetric
flasks with deionized water and used for ICP-OES analysis.
The characterization of extractable organic compounds present
in the sludge samples was carried out using a gas chro-
matograph/mass spectrometer (GC/MS, Shimadzu GC-2010, and
QP-2010, Shimadzu (Asia Pacific) Pte. Ltd., Singapore). Typically, 1
g of sludge was diluted with 20 mL of DCM solvent. A DB-5MS cap-
illary column (5%-phenyl-methylpolysiloxane, 30 m length ×0.25
mm i.d. × 0.25 ␮m film thickness) was used to separate the com-
pounds. High purity (5.5 grade) helium was used as the carrier gas
at a flow rate of 0.8 mL min−1 . The column oven temperature was
programmed as follows: isothermal at 45 ◦ C for 2 min, then heated
to 240 ◦ C at a ramp rate of 5 ◦ C min−1 , and finally maintained at
240 ◦ C for 2 min. The injector, MS ion source, and detector tem-
peratures were set at 275 ◦ C, 320 ◦ C and 150 ◦ C, respectively. The
volume of the sample injected was 10 ␮L. The mass-to-charge (m/z)
range was from 35 to 350 Da, and the mass spectra of 100 peaks
were considered for detailed analysis. All the identified compounds
had a match factor greater than 85 % with respect to the NIST library
of mass spectra. The area under the peaks in the GC/MS total ion
chromatogram (TIC) was determined, and the area% was calcu-
lated as the ratio of area under a specific peak to the area of all
the peaks in the TIC. This peak area% is also referred to as selectiv-
ity%. This was determined for all the organic compounds, and the
compounds were grouped according to the functional group cate-
gory. The same procedure was also adopted to analyze the organic
385
Table 1
Properties of catalysts used in the study.
H-ZSM-5 FCC
Particle type Extruded pellets Fine powder
Particle size 2 mm dia. × 4−12 mm length <0.5 mm
Specific surface area (m2 g−1 ) 478 109
Pore volume (cm3 g−1 ) 0.34 0.18
Pore diameter (nm) 2.9 6.6
Total acidity (mmol g−1 ) 1.78 NAa
a
Not Analyzed.
composition of pyrolysis oil from non-catalytic and catalytic MAP
experiments. Due to the viscous nature of the oil, it was diluted
with dichloromethane solvent at a dilution ratio of 1:3 (v/v) prior
to injection in GC/MS.
The higher heating values (HHVs) of the feedstocks were
measured using a bomb calorimeter (IKA C2000, IKA, Germany).
Proximate analysis was performed according to the ASTM
E1131−08 method in an automatic multiple sample TG analyzer
(2000 A, Navas Instruments, USA) by taking 0.5 g of sample. In
a typical procedure, the sample temperature was increased from
ambient to 110 ◦ C in inert atmosphere, and held at this temperature
until a constant mass was recorded. The mass loss was recorded as
moisture content. Volatile matter content was obtained by further
increasing the temperature to 900 ◦ C at a heating rate of 10 ◦ C
min−1 , and noting the mass loss. The gas ambience was switched
to air at 900 ◦ C, and the sample was held at this temperature until
constant mass was recorded. Thus, fixed carbon was determined
from the mass loss at this condition, and ash was determined using
the final mass of the residue.
Elemental CHNS analysis of the feedstock was performed
according to ASTM D5291 in an elemental analyzer (Thermo Flash
2000, Thermo Fisher Scientific, Austria) by taking 2−3 mg of sample.
The Fourier Transform Infra-Red (FTIR) spectra of the feedstocks
were collected in attenuated total reflectance mode (ATR) in Agi-
lent Cary 630 FTIR spectrometer (Agilent Technologies, USA) at 4
cm−1 resolution. The oil and char from MAP experiments were also
characterized using the same procedures for proximate, elemental,
HHV and FTIR analyses.
The non-condensable product gases from MAP experiments
were quantified by using two portable online analyzers connected
in parallel (Agasthya 2013 Series, Bhoomi Analyzers, India). The first
analyzer measured the concentrations of gases like NH3 , SO2 , HCl
and total hydrocarbons, while the second one was used to measure
the concentrations of O2 , CO, CO2 , CH4 and H2 in vol.% of the gas
stream. Electrochemical sensors were used for the detection of H2
and O2 , while non-dispersive infra-red sensors were used for the
quantification of CO, CO2, and CH4 .
2.2. Catalyst and susceptor characterization
H-ZSM-5 catalyst (Si:Al = 19) was procured from Riogen Catalyst
Inc., U.S.A. The regenerated FCC catalyst was provided by CPCL. Both
the catalysts were characterized using porosimetry (Micromeritics
ASAP 2020 V4). Nitrogen adsorption-desorption isotherms were
collected to determine the specific surface area, pore volume, and
average pore diameter. Ammonia-temperature programmed des-
orption method was used to determine the total acidity of the
H-ZSM-5 catalyst. The methodology is outlined in Suriapparao et al.
(2020). The regenerated FCC catalyst is basically a silica-alumina
catalyst. The properties of the catalysts are given in Table 1. Both
the catalysts were calcined in a muffle furnace at 600 ◦ C for 6 h
in air ambience before their use in experiments. The FTIR spectra
of the fresh, spent and regenerated catalysts were recorded in ATR
mode in a Cary 630 FTIR spectrometer (Agilent Technologies) at 4
cm−1 resolution.
386 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395
Fig. 1. Thermogravimetric and derivative thermogravimetric curves of (a) sludge 1, and (b) sludge 2. (c) FTIR spectra of sludge 1 and sludge 2.
Activated carbon (average particle size =1 mm) was procured
from S.D. Fine Chemicals Limited, India, and was used as a suscep-
tor. The specific surface area, pore size, and pore volume of activated
carbon were 450 m2 g−1 , 1.8 nm, and 0.19 cm3 g−1 , respectively.
Proximate analysis of ACS revealed that it contains ∼91 wt.% of fixed
carbon on a dry basis. From our previous studies, it is well estab-
lished that ACS susceptor does not decompose under the pyrolysis
conditions employed in the microwave reactor (Yerrayya et al.,
2018).
2.3. Microwave reactor setup
The schematic of the experimental set-up is shown in Fig. 2. The
test rig included an on-off type microwave oven, which was modi-
fied to carry out pyrolysis experiments. A hole of diameter 30 mm
was drilled at the rear of the oven to accommodate a cylindrical
adaptor, and sealed using a Teflon® cork. A provision for inserting
a metallic tube was made by drilling a hole into the Teflon® cork. A
K-type thermocouple was placed inside the metallic tube to mea-
sure the temperature of the reaction mixture during pyrolysis. The
construction of the thermocouple is provided in our earlier pub-
lications (Yerrayya et al., 2018; Suriapparao et al., 2020). Another
similar provision was made to purge inert N2 gas through the reac-
tion mixture, which also served as the make-up gas in experiments
involving catalytic upgradation of pyrolysates.
2.4. Experimental procedure
In non-catalytic pyrolysis experiments, 30 g of the sample was
taken in a custom-built cylindrical flask made of quartz, while in
experiments involving catalytic upgradation of vapors, 100 g of
sample was taken in a quartz flask with a round bottom and a wide
neck. A reducer was used to connect the cylindrical or round bottom
flask with the adaptor. As shown in the schematic, the exit of the
reactor section was connected to a vertical catalyst section, which
was 25 cm in length with a 5 cm inner diameter. The catalyst was
packed to a length of 10 cm from the bottom of the catalyst tube.
The packed catalyst tube was pre-heated to 400 ◦ C using a heating
tape connected to a temperature controller. The exit of the cat-
alyst tube was connected to a series of condensers to collect the
condensable vapors in the form of oil in the round bottom flasks.
Water was circulated at room temperature through the jacket of
the condensers. The outlet of the final oil collection flask was con-
nected to two online gas analyzers to determine the concentration
of non-condensable gases.
In a typical experiment, 27 g of crude sludge and 3 g of ACS were
mixed thoroughly using a laboratory blender. Few experiments
were also performed without the addition of susceptor, using 30 g
of crude sludge. All connection ports were sealed with at least two
layers of Teflon® tape to ensure that no leakage and contamination
of products occurred at any point in the set-up. The thermocouple
was placed into the feed mixture and sealed with Teflon® tape. The
required microwave power and time were set, and the experiment
was started. The temperature was noted during the microwave off-
time until the final temperature of 700 ◦ C was reached. At the end of
every experiment, the mass of char and oil were measured using an
analytical balance, and the mass of gas was calculated using mass
balance. While calculating the mass of char, the initial mass of ACS
was subtracted from the overall mass of the solid residue. Product
yields were calculated using the following equation.
Mass of product (oil or char) (g)
Product yield (%) = × 100 (1)
Mass of crude sludge (g)
A higher amount of feed of 100 g was used in catalytic experi-
ments, with a feed-to-catalyst mass ratio of 1:1. The weight hourly
space velocity (WHSV) of the vapors was calculated to be 1.9-4.5
h−1 owing to the different rates at which the vapors were gener-
ated by varying the microwave power. The actual mass flow rate
of vapors at different microwave powers are provided in Table S1
(in Supplementary Information). Nitrogen was used as a make-up
 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395 387

Fig. 2. Schematic of microwave pyrolysis and catalytic upgradation experimental set-up.

Table 2 samples is reflected in their HHVs. The analysis of metal ions in the
Characterization of crude oil sludge samples.
ash reveals that iron is a major constituent in both sludge samples.
Parameter Sludge 1 Sludge 2 Although the iron content in sludge 2 is high, as seen in Table 2,
Elemental analysis (wt.%, dba ) its concentrations in the ash fractions are strikingly similar (37.3
Nitrogen 0.5−2 8.4 ± 1.0 % in ash from sludge 1 and 37.1 % in ash from sludge 2). The pres-
Carbon 73.8 ± 1.5 39.4 ± 1.0 ence of iron as the major inorganic component of oily sludge is also
Hydrogen 11.3 ± 0.2 5.1 ± 0.3 reported by Chang et al. (2000). This is attributed to the corrosive
Sulphur 0.5−3 6.3 ± 1.0
action of crude oil during its transportation in steel pipelines and
Oxygenb 8.6−12.6 1.7
Proximate analysis (wt.%) storage in vessels. The concentrations of heavy metals like As, Cd,
Moisture (adc ) 9.8 4.4 Cr, Hg, Pb, and V are below the detectable limit (< 0.1 ppm), which
Volatiles (dafd ) 94.8 98.1 is in line with Indian effluent standards (Central Pollution Control
Fixed carbon (dafd ) 5.2 1.9
Board, 1986).
Ash (dba ) 1.3 39.1
Higher heating value (MJ kg−1 ) 36.0 19.6 From Fig. 3, it is evident that sludge 2 contains a high amount
ICP-OES analysis (wt.% of sludge) of aromatic compounds (27 %) as compared to that in sludge
Copper 0.0 0.1 1 (10.2 %). The aromatic fractions in both sludges were rich
Iron 0.4 13.9 in polycyclic aromatic hydrocarbons such as methyl-substituted
Mercury 0.0 0.1
derivatives of naphthalene, phenanthrene, azulene, chamazulene,
Aluminum NAe 1.0
Barium 0.004 0.1 and anthracene. Apart from this, sludge 1 contained a higher
a
amount of normal and iso-paraffins (74.3 %) than sludge 2 (41.5
dry basis.
b
O = 100-(C+H+N + S+Ash). %). The amount of olefins and naphthenes, on the other hand, was
c
Air dried basis. similar in both cases. Organic sulphur was exclusively present in
d
Dry ash free basis. the form of dimethyl dibenzothiophene and trimethyl benzothio-
e
Not Analyzed. phene in sludge 1. In sludge 2, a majority of sulphur was detected in
the form of octathiocane (S8 ) in addition to those sulfur compounds
gas at 500 LSTP min-1 . The catalyst bed was pre-heated and main- detected in sludge 1. In sludge 1, oxygen was present in the form of
tained at 400 ◦ C. The remainder of the procedure was the same as esters and long-chain alcohols. Sludge 2 contained oxygenates of
that of non-catalytic experiments, which is explained in the pre- similar functionality along with ethers and carboxylic acids. Nitro-
ceding paragraphs. The mass of coke was calculated by subtracting gen was present in the form of amino groups attached to aromatics
the mass of fresh catalyst (100 g) from that of the used catalyst at and long-chain carboxylic acids/esters in both feedstocks.
the end of the experiment. The TG mass loss profile of sludge 1 (Fig. 1(a)) suggests that the
first decomposition regime (170−400 ◦ C) comprises ∼40 % of the
organics in sludge 1. The second decomposition regime (400−500
3. Results and discussion ◦ C) is due to the cracking of heavier fractions which amounts to

∼46 % of organics in sludge 1. At the end of 800 ◦ C, almost 94.8 % of

3.1. Feedstock characterization
sludge 1 is decomposed. Sludge 2 exhibits a composite decomposi-
tion pattern in which two peaks at 250 ◦ C and 448 ◦ C are observed
From Table 2, it is evident that the volatile matter in sludge 2,
(Fig. 1(b)), and these accounted for 46.6 % of the sample mass. Unlike
on a dry basis, was 59.7 wt.%, while it was 88.3 wt.% in sludge 1.
sludge 1, the sample continued to decompose beyond 600 ◦ C and
Sludge 1 is superior owing to high amounts of carbon, hydrogen,
produced two additional decomposition peaks at 683 and 782 ◦ C,
and volatile matter in it, while sludge 2 is of a poor grade owing
which accounted for 10 % mass of the sample. The sample contin-
to a high amount of ash, nitrogen, and sulfur. This is clearly due
ued to degrade up to 985 ◦ C, with the residue accounting for 42.5 %
to the way these are sourced in the refinery, which was already
of the initial sample mass. Based on this, 700 ◦ C was chosen as the
discussed in section 2.1. The elemental composition of the sludge
388 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395

Fig. 3. Chemical composition of sludge 1 and sludge 2 obtained via solvent extraction.

final temperature for MAP experiments, as it would ensure maxi-

mum devolatilization of the samples. The salient vibrations in the
FTIR spectra (Fig. 1(c)) of the sludge samples include C−H asymmet-
ric/symmetric stretching (2917 cm−1 ) associated with methylene
CH2 − group, and C−H bending (1461 cm−1 ) associated with methy-
lene and methyl groups (Coates, 2006). Compounds like paraffins
and iso-paraffins fit well into this description. Aromatic compounds
are characterized by C=C−C ring stretching, C−H in-plane bending
and C−H out-of-plane bending vibrations, which are observed at
1605, 1030, and 719 cm−1 , respectively. These peaks are intense
in the case of sludge 2 as compared to sludge 1, which suggests
that the aromatic hydrocarbons are more substantial in the former.
This also validates the organic composition of the sludge samples
obtained from GC/MS analysis of the extractives.

3.2. Microwave pyrolysis of sludge samples

Sludge 1 was subjected to MAP without susceptor to determine

the time taken to achieve the final pyrolysis temperature of 700 ◦ C
due to the self-heating effect. It is evident from Fig. 4(a) that it took
34 min to achieve 700 ◦ C at 600 W microwave power. To accelerate
the heating rate of the sample, 10 % by mass of ACS was mixed with
sludge 1. It is clear that the final temperature was attained within
20 min with an average heating rate of 35 ◦ C min−1 . This is due
to the combined effect of chemically bound moisture in the crude
sludge, and the added susceptor. Fig. 4(a) shows that the heating
rate of sludge 1 is high in the initial period (297 ◦ C in 30 s), which is
due to the conversion of microwave radiation to heat through the
friction caused by the rotation of dipoles in the alternating electric
field among the polar water molecules trapped within the complex
matrix of the sludge. This caused the dissipation of heat through the
sample and allowed water to play the role of a susceptor in the ini-
tial stages of the experiment (Chandrasekaran et al., 2012; Kumar
and Mohan, 2013; Ratanadecho et al., 2002). Later, the carbona-
ceous char formed during this process, and the externally added
ACS, aided in pyrolyzing the sample. It is also observed that sludge
2 is pyrolyzed within 15 min at an average heating rate of 59 ◦ C
min−1 . This is due to the high ash in sludge 2, which is rich in Fe.
Fe, in powder form, is known to act as a susceptor and enhance the
rate of heating of the feedstock due to multiple internal reflections
Fig. 4. Temperature profiles from microwave pyrolysis of (a) sludge 1 and sludge
2 at 600 W with 10 % ACS loading, and sludge 1 at 600 W without ACS, (b) sludge
1 at 600 W with different ACS loading, and (c) sludge 1 with 10 % ACS loading at
different microwave powers.
of microwaves within the sample matrix (Suriapparao and Vinu,
2015).
The product yields from pyrolysis of sludge 1 and sludge 2 at
600 W power and 10 % ACS loading are presented in Fig. 5. Oil yield
from sludge 1 was high (87.3 %) as compared to that from sludge
2 (41.2 %), which is partly expected due to the characteristics of
the feedstocks. The high yield of the gas fraction (14.4 %) produced
from sludge 2 can be attributed to the increased severity of cracking
reactions caused by the inorganics present in it. When no ACS was
used, there was only a minor decrease in the yield of oil from sludge
1 (81.4 %) with a concomitant increase of char (8%). Nevertheless,
the use of ACS is important to accelerate the heating rate of the
sample, thereby reducing the processing time. The production of a
 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395 389

THCd

37.6

44.3
42.5
30.0
37.5
37.1
25.3
30.7
CH4
NH3

0.2
0.1
0.1
0.1
Average gas concentration (vol.%)

SO2

0.1
0.2
0.5
0.2
CO2

1.4
1.5
1.2
2.0
Characteristics of char and composition of non-condensable gases from MAP of sludge 1 at 450, 600, and 800 W with 10 % ACS loading, and sludge 2 at 600 W with 10 % ACS loading.

3.3
8.8
3.6
7.3
CO

Calculated using Channiwala’s formula: HHV (MJ kg−1 ) = 0.3491 × C + 1.1783×H – 0.1034 × O – 0.0151 × N + 0.1005 × S – 0.0211×Ash (Vargas-Moreno et al., 2012).
13.1

10.9
Fig. 5. Product yields from MAP experiments conducted with sludge 1 and sludge

4.9

6.8
H2
2 at different power ratings and ACS loading respectively.

HHV of charc
high amount of water due to dehydration reactions was observed

)
−1
in the oil fraction obtained from sludge 2. The moisture content

(MJ kg
in the oil produced from sludge 2 was 20.7 wt.%, which is nearly

24.6
25.9
28.4
3.8
50 % of the oil yield, while moisture in oil from sludge 1 was only
5%. The oil yield from sludge 2 using 10 % ACS loading at different
microwave powers followed the trend: 41.2 wt.% (600 W) ≈ 40.1

11.2±1.2
5.6±3.0
wt.% (800 W) > 35.3 wt.% (450 W).

6.7
2.0
b
The removal of oxygen from the feedstocks also occurred by the

O
elimination of CO and CO2 , which is shown in Table 3. At 600 W
microwave power and 10 % ACS loading, the evolution of CO, CO2 ,

3.5±1.3
5.0±1.6
H2 , and CH4 gases is more from sludge 1 as compared to sludge 2,

4.5
8.3
S
while the production of total hydrocarbons, including low molec-
ular weight (LMW) C2-C4 hydrocarbons, is more from pyrolysis of
Elemental analysis of char (wt.%, dba )

0.5±0.1
0.4±0.1
sludge 2. This shows that, owing to the high extent of pyrolysis
severity caused by rapid heating of the sample, sludge 2 is cracked

0.4
0.0
N
to a greater extent, which leads to an increase in LMW hydrocarbon
gases. The selective evolution of CO over CO2 can be attributed to
1.2±0.2
0.9±0.1
oxygen-deprived conditions at high temperatures, which can cause 0.8
0.4
the reduction of CO2 to CO through the reverse water gas reaction
H

in the presence of hydrogen. Similar trends have been reported for

pyrolysis of crude sludge by Huang et al. (2015) and Chen (2016),
69.4±1.6
75.2±1.5

and sewage sludge by Zhang et al. (2011). All the studies observed
13.4
79.0

increasing CO concentration as a result of high temperature (1000

C

◦ C) or increased susceptor loading of 15 % of granular activated

carbon. Traces of NH3 and SO2 were also detected .

Proximate analysis of char (wt.%, dba )

74.2±0.3
67.9±3.0

25.1±0.3

The composition of the solid residue, char, is also presented in

74.7

Table 3. Due to the high amount of ash in sludge 2, the char pro-
FC

duced from it is naturally low in elemental carbon, fixed carbon, and

HHV. However, char from sludge 1 is carbon-rich and possesses a
14.4±3.3
12.7±0.9

71.3±0.6

high HHV of 25.9 MJ kg−1 . The accumulation of fixed carbon in the

char samples is a result of carbonization that occurs at elevated
13.3
A

temperatures, after the devolatilization process (Menéndez et al.,

2010). Vdovenko et al. (2015) used differential thermal analysis
13.1±1.2
17.7±0.1

and showed that the process of carbonization can start as early as

3.6±0.4

480 ◦ C. More importantly, sulfur present in the feedstock is pre-

12.0
VM

dominantly captured in the char fraction. This can be attributed

to the fact that sulphur in the crude sludge exists in the form of
O = 100-(C+H+N + S+Ash).
Sludge 1, 450 W + 10 % ACS
Sludge 1, 600 W + 10 % ACS
Sludge 1, 800 W + 10 % ACS
Sludge 2, 600 W + 10 % ACS

dimethyldibenzothiophenes, which are difficult to crack at mod-

erate temperatures (≤ 700 ◦ C). These act as precursors for the
Total hydrocarbons.

carbonization reactions that lead to the build-up of aromaticity via

ring condensation. Fig. 6 shows the difference in the hydrocarbon
composition of oil obtained from the MAP of sludge 1 and sludge
dry basis.

2. Oil from sludge 1 is rich in paraffins and iso-paraffins, while

that from sludge 2 is rich in iso-paraffins and aromatic hydrocar-
Table 3

bons. The selectivity to naphthenes is similar in both the oils, while

a

olefins are more in the oil from sludge 1. The “Others” category
390 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395
Fig. 6. PIONA composition of oil from MAP of sludge 1 at 450, 600 and 800 W with
10 % ACS loading, and sludge 2 at 600 W with 10 % ACS loading.
depicted in Fig. 6 includes several organics with heteroatoms in
their structure. The dominant ones in this category include oxygen-
containing compounds like C12-C19 alcohols and long-chain esters
and ethers, followed by nitrogen-containing long-chain amines,
and sulfur-containing dimethylbenzothiophenes. The selectivity to
oxygen-containing compounds in the oil fraction from sludge 1 was
14.8 %, while it was 9.8 % in the oil fraction from sludge 2. The selec-
tivities to nitrogen-containing compounds in sludge 1 and sludge 2
were 0.4 % and 1.2 %, respectively. This emphasizes the importance
of catalytic upgradation to eliminate the oxygenates and other
hetero-atom-containing organics in the oil for fuel application.
3.3. Effect of susceptor loading and microwave power
Sludge 1 was chosen as the candidate feedstock to further
improve the characteristics of pyrolysis oil by altering the pro-
cess conditions and via catalytic upgradation. Fig. 4(b) shows the
temperature profiles attained when sludge 1 was pyrolyzed with
different amounts of ACS. It is evident that the time taken to reach
700 ◦ C was 10 min and 11 min when 50 % and 30 % loading of ACS
was employed, respectively. The average heating rate of the sam-
ple (in ◦ C min−1 ) followed the trend: 67 (50 % loading) > 60 (30 %
loading) > 35 (10 % loading). This is attributed to the microwave
absorbing ability of the activated carbon, which steadily enhances
the heating rate of the sample, especially beyond 200 ◦ C. The heat-
ing profile variations in the initial period up to 2 min are dominated
by the water molecules trapped in the sludge sample, whose expul-
sion occurs until around 200 ◦ C. Beyond this temperature, the role
of the susceptor is more significant, which leads to temperature
profiles following a specific trend. Fig. 4(c) shows the variation in
the heating profile of the sample at different microwave powers. As
expected, at 800 W, faster heating of the sample is achieved within
10 min at an average heating rate of 66 ◦ C min−1 , while at 450 W,
the heating rate is slower (32 ◦ C min−1 ). It is important to note
that the specific microwave power density, defined as the ratio of
microwave power to the mass of the sample, is 27 W g−1 , 20 W
g−1 and 15 W g−1 at 800 W, 600 W and 450 W, respectively. This
shows that heating of the sample is faster as the microwave power
is increased. It is worthwhile to mention that the sticky nature of the
sludge leads to heterogeneities in the distribution of trapped mois-
ture in it. From Fig. 4(c), it is evident that, in the temperature range
of 150−200 ◦ C, the heating achieved in the sample does not fol-
low a clear trend with microwave power. However, beyond 200 ◦ C,
which marks the decomposition of hydrocarbons, the temperature
profiles clearly follow a trend with microwave power.
Fig. 5 shows the product yields from experiments performed
using different ACS loading at 600 W and those performed at dif-
ferent microwave powers at 10 % ACS loading. It is clear that, with
an increase in ACS loading from 0% to 50 %, the yield of oil increases
initially and then decreases with maximum yield obtained at 10 %
loading of ACS. Owing to an increase in pyrolysis severity caused
by the addition of more ACS, a greater extent of cracking of hydro-
carbons occurs, and this leads to an increase in the production of
LMW hydrocarbon gases. A steady increase in the production of
the gaseous fraction substantiates this argument. The gas yield fol-
lows the trend: 18.2 wt.% (50 % ACS loading) > 10.2 wt.% (30 % ACS
loading) > 7.3 wt.% (10 % ACS loading). In a study by Chen (2016),
the use of 10 % granular activated carbon susceptor yielded a mini-
mum amount of char (8.3 %). In their study, activated carbon loading
below 10 % and above 10 % resulted in higher char yields. This is in
line with the results from this study, which prove that 10 % loading
of ACS yields a minimum amount of char (5.4 wt.%) with maximum
oil yield (87.3 wt.%). The effect of microwave power on product
yields from sludge 1 with 10 % loading of ACS is also depicted in
Fig. 5. At 450 W and 600 W, the oil yields were 84.2 ± 1.9 wt.% and
87.3 ± 5.2 wt.%, respectively, and can be considered to be similar.
The high yield of oil at 450 W can be attributed to the controlled
cracking reactions due to the longer off-time of the magnetron.
Increasing the microwave power to 800 W clearly decreased the
oil yield to 81 ± 2 wt.%, which is due to excessive cracking reac-
tions. This is substantiated by the slightly higher yield of gases. The
yield of char at different microwave powers followed the trend:
7.1 ± 0.1 wt.% (800 W) > 5.4 ± 2.0 wt.% (600 W) > 4.7 ± 0.5 wt.%
(450 W). This trend can be attributed to the increased amount of
coking and deposition of multi-ring aromatic hydrocarbons on ACS
due to higher heating rates in the samples (Chen, 2016). This is also
supported by the fact that the ACS used in this study had a higher
external surface area of 70 m2 g−1 , in addition to a higher micropore
area (380 m2 g−1 ).
The PIONA distribution in the oil fraction from experiments per-
formed at different microwave powers at 10 % loading of ACS is
depicted in Fig. 6. The detailed lists of organic compounds present
in the oil fraction are available in Tables S2, S3, and S4 (in Sup-
plementary Information). It is worthwhile to note that the PIONA
distribution in the solvent-extracted crude sludge followed the
trend: iso-paraffins (41 %) > paraffins (33 %) > aromatics (10 %)
> naphthenes (6%) > olefins (0.2 %). Due to the cracking of the
feedstock, the formation of iso-paraffins is reduced, while olefin
production is significant in the oil. This is clearly due to the free
radical elementary reactions involving ␤-scission of the long-chain
hydrocarbons, which leads to the production of terminal alkenes
(Vinu and Broadbelt, 2012). There is also a marginal increase in
olefin selectivity in the oil from 5% to 7% as the microwave power
is increased from 450 to 800 W. The major hydrocarbon type in the
pyrolysis oils includes paraffins, followed by iso-paraffins, aromat-
ics, olefins, and naphthenes. Most of the iso-paraffins belonged to <
C20, and were either mono methyl- or tetra methyl-substituted
alkanes. For example, 2,6,10,14-tetramethyl hexadecane was a
dominant iso-paraffin in the oil fraction from most of the exper-
iments. Naphthenes were mostly alkyl-substituted cyclohexanes,
with the length of the alkyl group being greater than ten. A clear
decrease in selectivity to paraffins was observed with an increase
in microwave power, which was accompanied by a slight increase
in selectivity to iso-paraffins. Syamsiro et al. (2013) observed an
increase in the production of iso-paraffins with increasing pyrol-
ysis temperature. This can be correlated, at least partially, to the
decrease in methane production with an increase in microwave
power to 800 W (Table 3). Methane production during microwave
pyrolysis is generally attributed to the recombination of methyl
and hydrogen radicals produced during pyrolysis (Reddy and Vinu,
2016; Reddy et al., 2019). Methyl radicals are usually produced
 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395 391

Table 4
Properties of pyrolysis oil from non-catalytic and catalytic MAP experiments using sludge 1. The catalyst loading is 100 g corresponding to WHSV of 1.9-4.5 h−1 .

Product fraction (selectivity %) HHVc Elemental analysis of oil (wt.%)

C8-C10 C10-C14 C15-C20 >C20 Aromatics Others MJ kg−1 C H N S Oa

Non-catalytic experiments
450 W, 10 % ACS 2.6 26.7 41.1 13.2 8.6 16.4 NAb NAb NAb NAb NAb NAb
600 W, 0% ACS 3.4 26.8 44.4 12.1 8.1 13.3 NAb NAb NAb NAb NAb NAb
600 W, 10 % ACS 2.9 25.3 44.5 11.7 7.3 15.6 42.4 79.4 13 2 BDLd 5.6
800 W, 10 % ACS 1.0 22.8 45.2 12.2 7.3 18.8 39.7 76.8 11.8 2.3 BDLd 9.1
Catalytic experiments
H-ZSM-5, 600 W 2.5 25.0 51.4 11.0 4.0 10.1 45.8 84.7 13.8 1.2 BDLd 0.3
H-ZSM-5, 800 W 3.3 23.8 52.4 10.2 5.3 10.3 44.9 83.7 13.5 1.1 BDLd 1.7
H-ZSM-5, 1100 W 9.8 22.2 44.1 15.0 11.4 8.9 42.4 80.5 12.6 1.6 BDLd 5.3
FCC, 800 W 9.6 30.4 42 7.5 16.6 10.5 NAb NAb NAb NAb NAb NAb
a
O = 100-(C+H+N + S).
b
Not Analyzed.
c
Calculated using Channiwala’s formula: HHV (MJ kg−1 ) = 0.3491 × C + 1.1783×H – 0.1034 × O – 0.0151 × N + 0.1005 × S – 0.0211×Ash (Vargas-Moreno et al., 2012).
d
Below Detectable Limit.

by end-chain fission of the hydrocarbon chain, and these can also

recombine with hydrocarbon free radicals on the secondary methy-
lene carbon to produce branched alkanes. The decrease in methane
production with an increase in microwave power shown in Table 3
justifies this argument.
The selectivity to aromatic hydrocarbons in the oil fraction
was 7–8 %. The major aromatic hydrocarbons in the oil frac-
tion include dimethyl- and trimethyl-substituted naphthalenes,
with traces of trimethyl- and tetramethyl-substituted benzene.
Other polycyclic aromatics were not detected in the oil fraction,
which suggests that these might have undergone condensation
reactions and retained the char fraction. Typically, naphthalene
derivatives are present in fuel oil and light cycle oil (LCO), while
transportation grade fuels like gasoline and high-octane gasoline
largely contain monoaromatics like BTEX (benzene, toluene, ethyl-
benzene, xylene). Therefore, the oil fraction is more suited for
fuel oil application or as a blendstock with LCO. In addition to
PIONA, hetero-atom-containing organics were also significant in Fig. 7. Product yields from catalytic upgradation of pyrolysis vapours from sludge 1
the oil fraction, which is shown in Fig. 6. Most of these were with H-ZSM-5 and FCC catalysts at 600, 800, 1100, and 800 W. The catalyst loading
is 100 g with WHSV of 1.9-4.5 h−1 .
oxygen-containing species such as long-chain alcohols, long-chain
esters, and methyl ethers. Some of these compounds also possessed
multiple functionalities such as 1-octadecanol, methyl ether. The gered by the expulsion of H radicals from alkane and phenyl groups
selectivities to oxygen-containing organics were 17.7 %, 14.8 %, and due to localized microplasma hot spots (Reddy et al., 2018). The H
15 % in the pyrolysis oils obtained at 800 W, 600 W, and 450 W, radicals can further recombine to form H2 in the gas phase. The
respectively. Sulfur-containing organics were nearly absent in the composition analysis of char shows that it is highly carbonized
oil fraction as they were probably trapped in the char, while traces when the microwave power is 800 W. The increase in carbon con-
(<1%) of nitrogen-containing long-chain hydrocarbon amines were tent and reduction in oxygen content in the char validates the
noticed. increase in its HHV as the microwave power is increased from 450
The presence of aliphatic and aromatic functional groups in W to 800 W. The high HHV of the chars (24−28 MJ kg−1 ) sug-
the oil fraction is also confirmed through FTIR analysis, which is gests that it can be re-used as a susceptor in microwave pyrolysis
shown in Fig. S1 (in Supplementary Information). Table 4 depicts experiments to enhance the heating rate. One of the concerns in
the carbon number distribution of hydrocarbons and elemental utilizing this char for heating applications is the high amount of
composition of oil from MAP experiments conducted at 450 W, 600 sulfur in it, which might cause SOx emissions upon combustion.
W and 800 W. It is important to note that the addition of 10 % ACS The analysis of metals in the char showed that it had retained all
at 600 W does not significantly alter the hydrocarbon distribution the elements that were originally present in the crude sludge (Table
in the oil fraction as compared to the case when no ACS was added S5 in Supplementary Information).
to the sludge sample. This proves that the major role of ACS is to
accelerate the rate of heating of the sample. It is evident that oxy- 3.4. Catalytic upgradation of pyrolysis vapors
gen content in the oil is slightly more than 5 wt.% in the oils from
MAP experiments conducted at 600 W and 800 W, which results Fig. 7 depicts the product yields from experiments in which
in 42.4 MJ kg−1 and 39.7 MJ kg−1 of HHV from these experiments, the pyrolysis vapors were passed through a catalyst bed contain-
respectively. ing H-ZSM-5 or FCC catalyst. The effect of catalyst loading on the
From the gas composition data shown in Table 3, it is clear catalytic upgradation process is reflected through the variation of
that the removal of oxygen occurred via decarbonylation and WHSV. Generally, a decrease in WHSV is equivalent to increasing
decarboxylation reactions. More importantly, LMW hydrocarbons the amount of catalyst thereby increasing the contact time of the
were eliminated from the long-chain paraffinic portion of the pyrolysates. In this study, WHSV variation in the range of 1.9-4.5
crude sludge during pyrolysis. The liberation of hydrogen during h−1 with H-ZSM-5 catalyst was achieved by varying the microwave
microwave pyrolysis of hydrocarbon fractions is known to get trig- power (600 W, 800 W, 1100 W), which affects the rate of genera-
392 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395
tion of pyrolysis vapors. When the rate of generation of vapors was
more at a high microwave power, the corresponding WHSV was
high (4.5 h−1 at 1100 W). This means the residence time of the
pyrolysates through the catalyst is relatively low. Such a variation
in residence time of the vapors through the catalyst bed is expected
to alter the upgraded oil composition. The WHSV used in this study
®
corresponds to typical values used in the IH2 process (Marker et al.,
2012; Venkatesan et al., 2020), and in the literature (Thring et al.,
2000; Carlson et al., 2011; Yildiz et al., 2015). It is worthwhile to
note that, at 1100 W, microwave delivery was continuous without
an off-time of the magnetron.
From Fig. 7, it is evident that the char yield increases with
an increase in microwave power, which is similar to the trend
observed in Fig. 5. Compared to experiments performed without
catalytic upgradation, the oil yield decreased after the upgradation
of vapors through the catalyst bed. This is due to the cracking and
deposition of small molecule pyrolysates within the pores of the
catalyst to form coke, which is in accordance with earlier studies
(Duman et al., 2013; Padmaja et al., 2009; Xie et al., 2014). The coke
yield is more from experiments involving higher WHSVs, which
corresponds to high microwave powers. At 800 W and 1100 W, the
coke yield was 24−27 wt.%, while at 600 W, the coke yield was low
(16 wt.%). Owing to low specific surface area and pore volume, coke
deposition on the FCC catalyst was low (11.5 wt.%) even at 800 W
microwave power.
Another important observation is the high yield of gases pro-
duced after the upgradation of vapors through the catalyst bed as
compared to the case without catalytic upgradation. This is due to
the reactions of pyrolysis vapors over the catalyst bed that facili-
tate the release of more non-condensable gases. Here, the residence
time dictates the extent of reactions, and hence, the yield of gases.
Better residence time, corresponding to low WHSV such as in the
case of 600 W (∼2 h−1 ) leads to a high yield of gases. The gaseous
fraction contained a significant amount of methane and C2-C6
gases, followed by hydrogen. For example, at 600 W microwave
power, the combined yield of methane and C2-C6 gases were ∼62
vol.% followed by H2 at 9 vol.% of the gaseous fraction. The con-
tent of CO and CO2 were typically lower than 1 vol.% in the exit gas
fraction, which suggests that these were possibly adsorbed in the
catalyst. A high yield of upgraded oil was obtained at 600 W using
the H-ZSM-5 catalyst (∼62 wt.%). Similar oil yield was obtained
(∼61 wt.%) with the FCC catalyst at 800 W.
Fig. 8 depicts the carbon number distribution of the upgraded
oil, classified according to PIONA. The detailed lists of organic com-
pounds present in the upgraded oil are available in Tables S6, S7,
S8, and S9 (in Supplementary Information). Several interesting fea-
tures, in terms of cracking of specific chain length molecules and
the origin of new functional groups, are evident from the figure.
Comparing the product distribution in Fig. 8(a) and (b), it can be
clearly stated that an increase in microwave power results in crack-
ing of C14 hydrocarbons to those in the C11-C13 range. Further
increase in microwave power to 1100 W results in the cracking of
C14-C19 fraction to form C8-C13 hydrocarbons (Fig. 8(c)). Experi-
ments with H-ZSM-5 catalyst produced a total selectivity of 80 %
to C7-C20 hydrocarbons, which was notably higher than that from
non-catalytic experiments (∼70 %). From Table 4, it is evident that
the C15-C20 hydrocarbons in the oil from experiments at 600 W
and 800 W with the H-ZSM-5 catalyst was higher than that from the
corresponding non-catalytic experiments. The formation of these
hydrocarbons can be attributed to cracking of > C20 hydrocarbons.
Interestingly, with the FCC catalyst, C8-C14 hydrocarbon selectiv-
ity is significant (∼40 %), which shows that this is also a promising
catalyst to control the carbon number distribution.
A steady increase in aromatic selectivity was observed with an
increase in microwave power. This is due to the cracking of linear
chain hydrocarbons at the Brönsted acid sites, and reactions such
as dehydrocyclization that lead to the conversion of linear chain
alkanes to cycloalkanes, and further into aromatic hydrocarbons.
The production of aromatics with H-ZSM-5 catalyst is well docu-
mented in the literature (Mihalcik et al., 2011; Suriapparao et al.,
2020; Xie et al., 2014). At temperatures below 500 ◦ C, a high degree
of cyclization of light paraffins and olefins can be expected when
H-ZSM-5 is used. Lee (2012) studied the effect of H-ZSM-5 cata-
lyst in the upgradation of paraffin wax, which was pyrolyzed in
a continuous fixed-bed reactor at 450 ◦ C for 1 h. The feedstock,
which contained 90 % paraffins and 10 % olefins, was converted to
18 % naphthenes and 77 % aromatic compounds. This shows that
the aromatic compounds are formed by the cyclization of olefins
to naphthenes, and dehydrogenation of naphthenes to aromatics
(Mullen and Boateng, 2010). Increasing the temperature enhances
the severity of cracking and aromatization reactions. Mihalcik et al.
(2011) obtained a high amount of alkylated aromatics in the oil via
catalytic fast pyrolysis of various biomasses with H-ZSM-5 at 550
◦ C. Olefins with terminal unsaturation are produced by the crack-
ing of paraffins and iso-paraffins at the acidic sites aided by protons
in the catalyst. Benzene rings undergo alkylation to produce aro-
matic rings with multiple substituents or can undergo bimolecular
Diels-Alder reaction with dienes to produce methyl-substituted
naphthalene derivatives (Mihalcik et al., 2011; Mullen and Boateng,
2010; Suriapparao et al., 2020).
One of the major observations that support the above mech-
anistic discussion is the composition of aromatics from catalytic
upgradation. Unlike the aromatics from non-catalytic experiments,
which were primarily methyl-substituted naphthalene derivatives,
the major aromatics in the oil fraction after catalytic upgradation
were ethylbenzene, xylenes, mesitylene (1,3,5-trimethyl benzene)
and ethyl methyl benzenes, while naphthalene derivatives and
polyaromatics were produced only in minor quantities. This is espe-
cially true in the case of oil from experiments conducted with
H-ZSM-5 at 1100 W and FCC at 800 W, in which aromatic selec-
tivities are significant. The influence of the pore size of the catalyst
is vital to understand the observed product distribution. The influ-
ence of large pore size of the catalyst in facilitating the diffusion
of bigger molecules is well documented in the literature (Syamsiro
et al., 2013; Uemichi et al., 1998). In this study, the pore size of
the FCC catalyst is nearly twice higher as that of H-ZSM-5. This
means that bigger reactant molecules can diffuse through the large
pores of the FCC catalyst, and react at the acidic active sites, while
they may not enter the small pores of H-ZSM-5. As a result, sig-
nificant reactions would occur only on the external surface of the
H-ZSM-5 catalyst. It is evident from Fig. 8(d) that better crack-
ing of pyrolysates, especially > C20 hydrocarbons, occurred with
the FCC catalyst, which ultimately resulted in the distribution of
hydrocarbons in the C8-C20 range. The C8-C10 hydrocarbons were
mostly alkyl-substituted monoaromatics. Lee (2012) demonstrated
catalytic upgradation of paraffin wax using FCC catalyst to control
the carbon number distribution in the C5-C12 range.
3.4.1. Product quality
Table 4 depicts the extent of deoxygenation achieved in the oil
fraction after catalytic upgradation. Consistently, the production of
hetero-atom-containing hydrocarbons is reduced (9–10 % selectiv-
ity) as compared to non-catalytic experiments. More importantly,
the elemental analysis of the oil fraction reveals that oxygen is sig-
nificantly lowered along with a marginal reduction in nitrogen, and
without any detectable sulfur. All these results in better HHV of
the oils (∼44−45 MJ kg−1 ), which is similar to transportation grade
fuels. This study shows that the upgraded oil can be successfully uti-
lized after mild hydrotreatment to meet the fuel specifications or
can be seamlessly blended with the refinery streams for hydropro-
cessing.
 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395
Fig. 8. Carbon number distribution of PIONA in upgraded oil from sludge 1 in C7 to C20 range at different conditions. (a) H-ZSM-5-600 W, (b) H-ZSM-5-800 W, (c) H-ZSM-
5-1100 W, and (d) FCC-800 W. The catalyst loading is 100 g with WHSV of 1.9-4.5 h−1 .
Fig. 9. Van Krevelen plot comparing the products of the current study to those from
the literature.
Fig. 9 shows the Van Krevelen plot comparing the quality of
products, in terms of H/C and O/C ratios, obtained in this study
with reference to conventional solid and liquid fuels, and fuels
obtained from different studies in the literature. Chen (2016) con-
ducted MAP of oily sludge using granular activated carbon as an
additive/catalyst, and produced pyrolysis oil containing 50 % selec-
tivity to hydrocarbons in the diesel range. However, the high atomic
O/C ratio (0.22) of the oil had a negative effect on its heating value,
which was ∼33 MJ kg−1 . The oil produced by Lam et al. (2012)
via MAP of waste automotive engine oils is shown to have a supe-
rior quality, though this can be attributed to the relatively low
amount of oxygenates in the feedstock. The role of catalytic upgra-
dation has been vital in improving the O/C ratio of pyrolysis oils
of the current study. Fig. 9 clearly indicates a shift in the quality
393
of pyrolysis-oil towards a diesel-like product due to the reduction
in its O/C ratio and minor improvement in the H/C ratio through
deoxygenation using HZSM-5 catalyst. Hu et al. (2017) conducted
the pyrolysis of petroleum sludge in an electrically heated fixed-bed
reactor to produce a high-grade product (O/C = 0.04 and H/C = 1.98)
with a relatively higher oxygen content (5%). Microwave heating is
more efficient as compared to conventional heating in the crack-
ing of heavy hydrocarbons including PAHs and asphaltenes to light
aliphatic and aromatic hydrocarbons.
A notable difference is observed in the O/C ratios of the chars
from experiments done with ACS. The effect of microwave power
on deoxygenation is clearly observed in the quality of chars from
sludge 1 as they tend to move closer to anthracite-quality coal. The
FTIR spectrum of the pyrolysis char showed no trace of organic
functionalities on its surface (Fig. S1 in Supplementary Informa-
tion). Nonetheless, the presence of metals in char (Table S5 in
Supplementary Information) should not be ignored, as it will deter-
mine its final application.
3.4.2. Characterization of spent catalysts
Fig. 10 shows the salient peaks in the FTIR spectra of fresh
catalysts, cokes/spent catalysts, and regenerated catalysts. The sig-
nificant peaks include the stretching vibrations of T−O−T (T = Si
and Al) in the range of 1250 to 950 cm−1 , which is characteris-
tic of the silica-alumina framework structure. The vibrations in the
range of 969−400 cm−1 can be attributed to the stretching of Si−O,
and that around 676 cm−1 to Al−O. It is generally observed that
a number of peaks corresponding to different organic functionali-
ties are evident in the FTIR spectrum of coke from the FCC catalyst
than HZSM-5. The broad peaks at higher wavenumbers showed
the presence of adsorbed moisture in the pores of the catalyst. The
high production of aromatic hydrocarbons using the FCC catalyst
resulted in significant number of peaks associated with mono- and
di-substituted aromatic rings, along with various aromatic-related
394 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395
Fig. 10. FTIR spectra of fresh catalyst, coke, and regenerated catalyst from catalytic upgradation experiments with (a) FCC catalyst and (b) HZSM-5 catalyst at 800 W.
frequencies in the range of 1225−950 and 900−690 cm−1 , in the
coke. Oxygen- and sulfur-containing moieties were also found on
the surface of the FCC catalyst, which suggests that the mode of
adsorption of reactants and intermediates on the surface of these
two catalysts may be different. Although a high yield of coke was
obtained from the HZSM-5 catalyst, the extent of aromatization
was low, which only led to the accumulation of methylene groups
on its surface.
The spent catalyst was regenerated by calcining at 600 ◦ C for
5 h in air ambience. It is evident from Fig. 10 that the functional
groups corresponding to coke were completely removed after calci-
nation. Importantly, the regeneration process was not detrimental
to the Si/Al framework of the catalysts. Duman et al. (2013) stud-
ied the regeneration of FCC catalyst for over 10 cycles, and showed
that the decrease in oil yield and weight loss of the catalyst were
minimal and close to zero. Yildiz et al. (2015) showed that, after
about 8 regeneration cycles, a difference in the quality of the oil as
compared to that using the fresh catalyst was observed. This cor-
responded to H/C ratio of the fuel dropping from 1.48 to 1.43, and
the yield of micro carbon residue increasing to 3.42 from 2.5.
4. Conclusions
This study has showcased the production of valuable hydro-
carbons from crude sludge, a major refinery waste, through
microwave-assisted pyrolysis technique. A detailed characteriza-
tion of the two sludge samples revealed that they are complex
feedstocks owing to the significant presence of oxygen-, sulfur-
and nitrogen-containing organics, and metallic constituents like
Fe in the inorganic fraction. Accordingly, sludge 1 was identified
as a good candidate for recovering maximum liquid hydrocarbons.
The optimal process condition that yielded maximum oil of ∼87
wt.% from sludge 1 was 600 W microwave power and 10 % loading
of activated carbon susceptor. Higher loading of the susceptor and
higher microwave power reduced the yield of oil while increasing
the production of gases, which is attributed to excessive cracking
of the long-chain hydrocarbons to C1-C5 gases. At this operating
condition, the oil yield from sludge 2 was ∼41 wt.%. Paraffins, iso-
paraffins, and olefins constituted a major fraction of the oil from
sludge 1 with a combined selectivity of ∼74 %, while the oil from
sludge 2 was rich in aromatic hydrocarbons whose selectivity was
∼41 %.
To reduce the oxygen content in the oil from sludge 1, and to
contain the carbon number distribution in the C8-C20 range, the
pyrolysis vapors were upgraded by passing them through a bed
of HZSM-5 and FCC catalyst in separate experiments by maintain-
ing a WHSV of 1.9-4.5 h−1 . Significant enhancement in C15-C20
hydrocarbons and a substantial reduction in oxygen content (<2
wt.%) were achieved with the HZSM-5 catalyst corresponding to
microwave powers of 600 and 800 W. The HHVs of the oils were also
high (44−45 MJ kg−1 ). The use of the FCC catalyst, corresponding to
pyrolysis at 800 W, promoted the formation of methyl-substituted
monoaromatic hydrocarbons via dehydrocyclization while improv-
ing the hydrocarbons in the C10-C14 range.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
The corresponding author thanks Chennai Petroleum Corpora-
tion Limited, Chennai, for providing the crude sludge samples, and
for funding this study. The authors thank Sophisticated Analytical
Instrument Facility, and the Department of Physics, IIT Madras, for
their assistance in ICP-OES and porosimetry analyses. The National
Centre for Combustion Research and Development is funded by
Department of Science and Technology, Government of India.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in
the online version, at doi:https://doi.org/10.1016/j.psep.2020.08.
025.
 P. Francis Prashanth et al. / Process Safety and Environmental Protection 146 (2021) 383–395
References
Bell, C., 2015. The Crude Oil Sludge Problem. https://www.bicmagazine.com/
industry/tank-term-storage/the-crude-oil-sludge-problem/.
Bhattacharyya, J.K., Shekdar, A.V., 2003. Treatment and disposal of refinery sludges:
indian scenario. Waste Manag. Res. 21, 249–261.
Carlson, T.R., Cheng, Y.T., Jae, J., Huber, G.W., 2011. Production of green aromatics
and olefins by catalytic fast pyrolysis of wood sawdust. Energy Environ. Sci. 4,
145–161.
Central Pollution Control Board, 1986. The Environment (Protection) Rules,
The Gazette of India. 19th November 1986. Notification No. S.O. 844
(E) (accessed May 2020) http://www.lawsindia.com/Industrial%20Law/
k57.htm#sSCHEDULE V. Central Statistics Office, 2019. Energy Statistics
2019 (twenty Sixth Issue) Central Statistics Office. Ministry of Statis-
tics and Programme Implementation Government of India, New Delhi,
http://mospi.nic.in/sites/default/files/publication reports/EnergyStatistics
2019-finall.pdf (accessed May 2020).
Chandrasekaran, S., Ramanathan, S., Basak, T., 2012. Microwave material processing-
a review. AIChE J. 58, 330–363.
Chang, C.Y., Shie, J.L., Lin, J.P., Wu, C.H., Lee, D.J., Chang, C.F., 2000. Major products
obtained from the pyrolysis of oil sludge. Energy Fuels 14, 1176–1183.
Chen, Y.R., 2016. Microwave pyrolysis of oily sludge with activated carbon. Environ.
Technol. 37, 3139–3145.
Coates, J., 2006. Interpretation of infrared spectra, a practical approach. In: Encyclo-
pedia of Analytical Chemistry., pp. 10815–10837.
Domínguez, A., Menéndez, J.A., Inguanzo, M., Pís, J.J., 2006. Production of bio-fuels by
high temperature pyrolysis of sewage sludge using conventional and microwave
heating. Bioresour. Technol. 97, 1185–1193.
Duman, G., Pala, M., Ucar, S., Yanik, J., 2013. Two-step pyrolysis of safflower oil cake.
J. Anal. Appl. Pyrolysis 103, 352–361.
Hu, J., Gan, J., Li, J., Luo, Y., Wang, G., Wu, L., Gong, Y., 2017. Extraction of crude oil from
petrochemical sludge: characterization of products using thermogravimetric
analysis. Fuel 188, 166–172.
Huang, Q., Wang, J., Qiu, K., Pan, Z., Wang, S., Chi, Y., Yan, J., 2015. Catalytic pyrolysis of
petroleum sludge for production of hydrogen-enriched syngas. Int. J. Hydrogen
Energy 40, 16077–16085.
Iisa, K., French, R.J., Orton, K.A., Yung, M.M., Johnson, D.K., Dam, J.T., Watson, M.J.,
Nimlos, M.R., 2016. In situ and ex situ catalytic pyrolysis of pine in a bench-scale
fluidized bed reactor system. Energy Fuels 30, 2144–2157.
Islam, B., 2015. Petroleum sludge, its treatment and disposal: a review. Int. J. Chem.
Sci. 13, 1584–1602.
Jiang, L., Wang, Y., Dai, L., Yu, Z., Wu, Q., Zhao, Y., Liu, Y., Ruan, R., Ke, L., Peng,
Y., Xia, D., Jiang, L., 2020. Integrating pyrolysis and ex-situ catalytic reform-
ing by microwave heating to produce hydrocarbon-rich bio-oil from soybean
soapstock. Bioresour. Technol. 302, 122843.
Johnson, O.A., Affam, A.C., 2019. Petroleum sludge treatment and disposal: a review.
Environ. Eng. Res. 24, 191–201.
Karayildirim, T., Yanik, J., Yuksel, M., Bockhorn, H., 2006. Characterisation of products
from pyrolysis of waste sludges. Fuel 85, 1498–1508.
Kumar, B., Mohan, B.R., 2013. Petroleum oily sludge and the prospects of microwave
for its remediation. Int. J. Eng. Res. Technol. 2, 359–370.
Lam, S.S., Chase, H.A., 2012. A review on waste to energy processes using microwave
pyrolysis. Energies 5, 4209–4232.
Lam, S.S., Russell, A.D., Chase, H.A., 2010. Microwave pyrolysis, a novel process for
recycling waste automotive engine oil. Energy 35, 2985–2991.
Lam, S.S., Russell, A.D., Lee, C.L., Chase, H.A., 2012. Microwave-heated pyrolysis of
waste automotive engine oil: influence of operation parameters on the yield,
composition, and fuel properties of pyrolysis oil. Fuel 92, 327–339.
Lee, K.H., 2012. Effects of the types of zeolites on catalytic upgrading of pyrolysis
wax oil. J. Anal. Appl. Pyrolysis 94, 209–214.
Mahari, W.A.W., Zainuddin, N.F., Nik, W.M.N.W., Chong, C.T., Lam, S.S., 2016. Pyrol-
ysis recovery of waste shipping oil using microwave heating. Energies 9, 1–9.
Marker, T., Felix, L., Linck, M., Roberts, M., 2012. Integrated Hydropyrolysis and
Hydroconversion (IH2) for the direct production of gasoline and diesel fuels or
blending components from biomass, Part 1: proof of principle testing. Environ.
Prog. Sustain. Energy 31, 191–199.
Menéndez, J.A., Arenillas, A., Fidalgo, B., Fernández, Y., Zubizarreta, L., Calvo, E.G.,
Bermúdez, J.M., 2010. Microwave heating processes involving carbon materials.
Fuel Process. Technol. 91, 1–8.
Mihalcik, D.J., Mullen, C.A., Boateng, A.A., 2011. Screening acidic zeolites for catalytic
fast pyrolysis of biomass and its components. J. Anal. Appl. Pyrolysis 92, 224–232.
Motasemi, F., Afzal, M.T., 2013. A review on the microwave-assisted pyrolysis tech-
nique. Renew. Sustain. Energy Rev. 28, 317–330.
Mullen, C.A., Boateng, A.A., 2010. Catalytic pyrolysis-GC/MS of lignin from several
sources. Fuel Process. Technol. 91, 1446–1458.
395
Olazar, M., Aguado, R., Bilbao, J., Barona, A., 2000. Pyrolysis of sawdust in a conical
spouted-bed reactor with a HZSM-5 catalyst. AIChE J. 46, 1025–1033.
Padmaja, K.V., Atheya, N., Bhatnagar, A.K., Singh, K.K., 2009. Conversion of Calotropis
procera biocrude to liquid fuels using thermal and catalytic cracking. Fuel 88,
780–785.
Ratanadecho, P., Aoki, K., Akahori, M., 2002. Influence of irradiation time, particle
sizes, and initial moisture content during microwave drying of multi-layered
capillary porous materials. J. Heat Transfer 124, 151–161.
Reddy, B.R., Vinu, R., 2016. Microwave assisted pyrolysis Indian and Indonesian coals
and product characterization. Fuel Process. Technol. 154, 96–103.
Reddy, B.R., Vinu, R., 2018. Microwave-assisted co-pyrolysis of high ash Indian coal
and rice husk: product characterization and evidence of interactions. Fuel Pro-
cess. Technol. 178, 41–52.
Reddy, B.R., Shravani, B., Das, B., Dash, P.S., Vinu, R., 2019. Microwave-assisted and
analytical pyrolysis of coking and non-coking coals: comparison of tar and char
compositions. J. Anal. Appl. Pyrolysis 142, 104614.
Shie, J.L., Chang, C.Y., Lin, J.P., Wu, C.H., Lee, D.J., 2000. Resources recovery of oil
sludge by pyrolysis: kinetics study. J. Chem. Technol. Biotechnol. 75, 443–450.
Shie, J.L., Lin, J.P., Chang, C.Y., Shih, S.M., Lee, D.J., Wu, C.H., 2004. Pyrolysis of oil sludge
with additives of catalytic solid wastes. J. Anal. Appl. Pyrolysis 71, 695–707.
Suriapparao, D.V., Vinu, R., 2015. Bio-oil production via catalytic microwave
pyrolysis of model municipal solid waste component mixtures. RSC Adv. 5,
57619–57631.
Suriapparao, D.V., Vinu, R., Shukla, A., Haldar, S., 2020. Effective deoxygenation for
the production of liquid biofuels via microwave assisted co-pyrolysis of agro
residues and waste plastics combined with catalytic upgradation. Bioresour.
Technol. 302, 122775.
Syamsiro, M., Hu, W., Komoto, S., Cheng, S., Noviasri, P., Prawisudha, P., Yoshikawa,
K., 2013. Co-production of liquid and gaseous fuels from polyethylene and
polystyrene in a continuous sequential pyrolysis and catalytic reforming system.
Energy Environ. Res. 3, 90–106.
Thring, R.W., Katikaneni, S.P.R., Bakhshi, N.N., 2000. Production of gasoline range
hydrocarbons from Alcell lignin using HZSM-5 catalyst. Fuel Process. Technol.
62, 17–30.
Tripathi, A.K., Ojha, D.K., Vinu, R., 2015. Selective production of valuable hydrocar-
bons from waste motorbike engine oils via catalytic fast pyrolysis using zeolites.
J. Anal. Appl. Pyrolysis 114, 281–292.
Uemichi, Y., Hattori, M., Itoh, T., Nakamura, J., Sugioka, M., 1998. Deactivation behav-
iors of zeolite and silica-alumina catalysts in the degradation of polyethylene.
Ind. Eng. Chem. Res. 37, 867–872.
Vargas-Moreno, J.M., Callejón-Ferre, A.J., Pérez-Alonso, J., Velázquez-Martí, B., 2012.
A review of the mathematical models for predicting the heating value of biomass
materials. Renew. Sustain. Energy Rev. 16, 3065–3083.
Vdovenko, S., Boichenko, S., Kochubei, V., 2015. Composition and properties of
petroleum sludge produced at the refineries. Chem. Chem. Technol. 9, 257–260.
Venkatesan, K., Prashanth, F., Kaushik, V., Choudhari, H., Mehta, D., Vinu, R., 2020.
Evaluation of pressure and temperature effects on hydropyrolysis of pine saw-
dust: pyrolysate composition and kinetics studies. React. Chem. Eng., http://dx.
doi.org/10.1039/D0RE00121J.
Vinu, R., Broadbelt, L.J., 2012. Unraveling reaction pathways and specifying reaction
kinetics for complex systems. Annu. Rev. Chem. Biomol. Eng. 3, 29–54.
Wan, Y., Chen, P., Zhang, B., Yang, C., Liu, Y., Lin, X., Ruan, R., 2009. Microwave-
assisted pyrolysis of biomass: catalysts to improve product selectivity. J. Anal.
Appl. Pyrolysis 86, 161–167.
Wang, K., Johnston, P.A., Brown, R.C., 2014. Comparison of in-situ and ex-situ cat-
alytic pyrolysis in a micro-reactor system. Bioresour. Technol. 173, 124–131.
Xie, Q., Peng, P., Liu, S., Min, M., Cheng, Y., Wan, Y., Li, Y., Lin, X., Liu, Y., Chen, P.,
Ruan, R., 2014. Fast microwave-assisted catalytic pyrolysis of sewage sludge for
bio-oil production. Bioresour. Technol. 172, 162–168.
Yerrayya, A., Suriapparao, D.V., Natarajan, U., Vinu, R., 2018. Selective production
of phenols from lignin via microwave pyrolysis using different carbonaceous
susceptors. Bioresour. Technol. 270, 519–528.
Yildiz, G., Ronsse, F., Venderbosch, R., Duren, Rvan, Kersten, S.R.A., Prins, W., 2015.
Effect of biomass ash in catalytic fast pyrolysis of pine wood. Appl. Catal. B:
Environ. 168–169, 203–211.
Zhang, B., Xiong, S., Xiao, B., Yu, D., Jia, X., 2011. Mechanism of wet sewage sludge
pyrolysis in a tubular furnace. Int. J. Hydrogen Energy 36, 355–363.
Zhang, Y., Cui, T., Liu, S., Fan, L., Zhou, N., Peng, P., Wang, Y., Guo, F., Min, M., Cheng, Y.,
Liu, Y., Lei, H., Chen, P., Li, B., Ruan, R., 2020. Fast microwave-assisted pyrolysis
of wastes for biofuels production – a review. Bioresour. Technol. 297, 122480.