A study on biofuel produced by catalytic cracking of mustard and castor oil

Prévia do material em texto

Science of the Total Environment 757 (2021) 143781
Contents lists available at ScienceDirect
Science of the Total Environment
j ourna l homepage: www.e lsev ie r .com/ locate /sc i totenv
A study on biofuel produced by catalytic cracking of mustard and castor
oil using porous Hβ and AlMCM-41 catalysts
Ramya Ganesan a, Shanthi Subramaniamb, Ravichandran Paramasivamc, Jamal S.M. Sabir d,
J.S. Femilda Josephin e, Kathirvel Brindhadevi f,⁎, Arivalagan Pugazhendhi g
a Department of Chemistry, St. Joseph's Institute of Technology, Chennai 600 119, India
b Department of Chemistry, Anna Adarsh College for Women, Chennai 600 040, India
c Department of Mechanical Engineering, St. Joseph's Institute of Technology, Chennai 600 119, India
d Centre of Excellence in Bionanoscience Research, King Abdulaziz University (KAU), Jeddah 21589, Saudi Arabia
e Department of Software Engineering, SRM Institute of Science and Technology, Kattankulathur 603 203, Tamil Nadu, India
f Institute of Research and Development, Duy Tan University, Da Nang 550000, Viet Nam
g Innovative Green Product Synthesis and Renewable Environment Development Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho ChiMinh City, Viet Nam
H I G H L I G H T S G R A P H I C A L A B S T R A C T
• Used vegetable oils from II generation
biomass were chosen for production of
biofuels.
• Microporous (Hβ) and mesoporous cat-
alysts (AlMCM-41) were synthesized,
characterized.
• Fixed bed catalytic cracking of castor oil
yielded 85% bio liquid products.
• ASTM standards were well obeyed by
the biofuel and hence projecting it for
commercial utility.
⁎ Corresponding author.
E-mail addresses: kathirvelbrindhadevi@duytan.edu.vn
https://doi.org/10.1016/j.scitotenv.2020.143781
0048-9697/© 2020 Elsevier B.V. All rights reserved.
a b s t r a c t
a r t i c l e i n f o
Article history:
Received 3 September 2020
Received in revised form 20 October 2020
Accepted 31 October 2020
Available online 16 November 2020
Editor: Huu Hao Ngo
Keywords:
Biofuel
Catalytic cracking
Castor oil
Hβ
AlMCM-41
Biofuel is the only novel solution to the increase in the greenhouse effect and bursting energy demand. The cat-
alytic cracking of non-edible vegetable oils, namely castor andmustard was studied to yield gasoline range (C5–
C9) hydrocarbons. Hβ (Microporous; pore size <2 nm) and AlMCM-41 (Mesoporous; pore size 2 nm–50 nm)
materials with different Si/Al ratios were used as catalysts for cracking purposes. Characterization of these cata-
lystswas done by X-ray diffraction, Surface area analyzer, nitrogen sorption studies, TPD and inductively coupled
plasma techniques. Used mustard oil was cracked over AlMCM-41 catalysts in a fixed bed catalytic cracking unit
at optimized reaction condition (400 °C, 4.6 h−1) obtained over Hβ. The liquid and gaseous products were ana-
lyzed using gas chromatograph (ShimadzuGC-9A). Among themesoporous catalysts AlMCM-41 (27)was able to
convert 75% of mustard oil into 48% of bioliquid and 30.4% selectivity towards BG. Pongamia, neem, castor, fresh
coconut and used coconut oil was also cracked using AlMCM-41 (27) catalyst. Themajor products of cracking re-
actions were Castor Bioliquid (CBL) comprising of bio gasoline (BG), bio kerosene (BK) and bio diesel (BD) with
less yield of gaseous products. AlMCM-41 converted 98% of castor oil into 85% of CBL and itwas testedwith ASTM
6751 standard procedures for its calorific value, viscosity and flash point. The sulphur emission from CBL run en-
gine reached lower index. The results exhibited the commercial utility of the CBL in the near future.
© 2020 Elsevier B.V. All rights reserved.
(K. Brindhadevi), arivalagan.pugazhendhi@tdtu.edu.vn (A. Pugazhendhi).
http://crossmark.crossref.org/dialog/?doi=10.1016/j.scitotenv.2020.143781&domain=pdf
https://doi.org/10.1016/j.scitotenv.2020.143781
mailto:kathirvelbrindhadevi@duytan.edu.vn
mailto:arivalagan.pugazhendhi@tdtu.edu.vn
https://doi.org/10.1016/j.scitotenv.2020.143781
http://www.sciencedirect.com/science/journal/
www.elsevier.com/locate/scitotenv
R. Ganesan, S. Subramaniam, R. Paramasivam et al. Science of the Total Environment 757 (2021) 143781
1. Introduction
The problems posed to present day's world are themuster of energy
demand, pollution caused by automobile exhaust and economic infla-
tion due to the energy imbalance across the countries (Goh et al.,
2019; Mona et al., 2020; Pollitt et al., 2019). The craving for energy
will be everlasting and the drive from transportation sectorwill escalate
in near future. Todays' fuel supply is mainly dominated by oil and gaso-
line is more in need. The energy for transportation alone consumes
about 38% of petroleum, followed by the industrial sector, which con-
sumes about 14% of petroleum (Ganesan et al., 2020). For the transpor-
tation purpose, liquid biofuel is necessary because the gaseous fuels face
the problem of transportation and safe handling (Ramírez et al., 2019).
In 2013, carbon emission was estimated as 9780 million MT and this is
like ironing the fire; global warming (Kumari and Singh, 2018; Javed
et al., 2020). These critical challenges have largely sparked the pursuit
of a fuel which could serve as the perfect alternate to the fossil fuels
(Orjuela and Clark, 2020; Banu et al., 2020). The perspectives of an alter-
nate fuel should be sustainable and society friendly that can be signified
as S2 (Junne and Kabisch, 2017). The only source capable of producing
such a fuel should be biomass and hence the fuel is well known as bio-
fuel. In this context, biofuel production from vegetable oils has drawn a
wide interest among researchers recently (Pechout et al., 2019; Wong
et al., 2020; Sadeek et al., 2020; Dhanya et al., 2020). Employment of
both edible and non -edible vegetable oils and seeds has created a
niche in biofuel industry that had been extensively reported (Wu
et al., 2019; Cao et al., 2019; Machacon et al., 2001; Mitrović et al.,
2020; Acharya et al., 2019). The various techniques practiced to gener-
ate biofuel are transesterification processed using large quantity of alco-
hol, pyrolysis performed at very high temperature, enzymatic
hydrolysis operated at high cost and catalytic cracking in presence of
catalyst (Ambat et al., 2018). The alkyl esters procured from
transesterification reaction termed as biodieselmay not be fed in engine
without blending with commercial diesel (Niculescu et al., 2019). Ac-
countable oxygenates present in the liquid retards the combustion pro-
cess which aids to choking of the automobile (Kumar et al., 2016).
Thermal cracking or pyrolysis converts the feedstock into liquid fuels
known as bio oil which is rich in only linear chain aliphatics and the
major drawback is the excessive energy drawn by high temperature in-
puts (Akah et al., 2019). Bio alcohol synthesized in enzymatic method is
sophisticated and extends the cost of reaction (Han et al., 2020). Com-
paratively, it is an acknowledged fact that catalytic cracking method is
superior over other techniques for the following reasons. The resilient
advantages of this method are a) appreciable low temperature to
work (less than 500 °C), b) higher oil feed to catalytic frame ratio,
c) yields high octane gasoline which burns cleanly, d) reduces the % of
higher hydrocarbon fuel oils, e) also isomerizes smaller gaseous frag-
ments into gasoline range hydrocarbons and last but not the least,
f) the fuel can be utilized in the absence of blends as it is purely hydro-
carbons (Yigezu and Muthukumar, 2014; Chen and Wang, 2019).
Broadly, porous materials are envisaged as potential catalyst in biofuel
production by virtue of a) their porous structure, b) high thermal stabil-
ity and, c) acidic nature. Microporous materials like 10membered ring-
ZSM-5, 12membered ring – β and Y, have beenwidely used as cracking
catalysts due to their excellent properties such as acidity and shape se-
lectivity (Perego et al., 2017). However, the small pores of the micropo-
rous catalysts curb the entryof triglyceride fragments to the zeolites
having strong acidic sites. Thus, molecules can react at the peripheral
acidic site of catalysts alone leading to lesser conversion. Mesoporous
catalyst MCM-41 discovered by mobil coworkers with a pore size of
2–50 nm has a 2 dimensional hexagonal symmetry and regular pore
channels demonstrates a typical pore size of 2.5 to 4.5 nm.With respect
to cracking, its large pore facilitates the reaction involving large mole-
cules. As a cracking catalyst their barriers are poor hydrothermal stabil-
ity and lowacidity (Wu et al., 2019). The introductionof aluminium ions
into its framework increases its acidity besides enhancing its
2
hydrothermal stability strengthens its characteristic as cracking cata-
lyst. This research work aimed to explore the probability of obtaining
biofuel through catalytic cracking of mustard, castor, pongamia, neem,
fresh and used coconut oils. In some parts of the world, mustard also
has been used for cooking purposes and the plant comprises of 6% satu-
rated hydrocarbon chains and can yield 30% oil. It is well-adapted to
marginal and arid regions because it is drought-resistant. Castor plant
grows well in tropical areas like Brazil, China and India. The oil yield is
around 30% to 50% and is vastly used in cosmetics. Pongamia pinnata is
an inhabitant of Asia, Australia and Pacific Islands. It is regarded as a
good alternative to jatropha oil for biofuel production with 32% to 42%
of oil content. Neem and coconut are rich in saturated fatty acids
Palmitic and Lauric acid respectively. Dorado et al. (2004) reported
transesterification of mustard oil and estimated lower concentrations
of NOX emitted using biodiesel produced frommustard oil with respect
to diesel fuel. A mixture of biodiesel derived from neem and pongamia
oil was Transesterified and tested in engines (Nagaraj et al., 2020). Cal-
cium oxide (CaO) prepared from waste biomass was used in biodiesel
production from neem oil (Adepoju, 2020). Catalytic pyrolysis of
neem oil using K2CO3 was reported by Mishra and Mohanty (2018).
Fly ash derived ZSM-5 catalystwas investigated in converting pongamia
oil into bio oil by fast pyrolysis (Soongprasit et al., 2019). High grade co-
conut oil was cracked over ZSM-5 catalyst in a microwave reactor (Wei
et al., 2020). At the optimized conditions obtained usingHꞵ in the crack-
ing of the mustard oil; reactions were done over AlMCM-41 of different
Si/Al ratios and the results were compared with Hβ.The better working
catalyst was tried on other oils and castor oil showed remarkable con-
version into liquid fuels and high selectivity of gasoline fraction.
AlMCM-41 (27) favored 88% conversion of castor oil into 68% of liq-
uid products and Hβ showed 75% conversion into 48% of liquid product.
The characteristics of derived fuel on testing with various ASTM stan-
dard methods give a promising approach for the quest for future fuel.
2. Materials and methods
2.1. Materials
A nearby market was chosen to buy all the oils employed in experi-
ment. The used oil was procured from local restaurants. The solid parti-
cles and dust were removed from oil by filtration and a proper refining
process is necessary to remove Phospholipids can be removed by and
hence all the collected oils were refined in Kallesuwari Refinery plant,
Chennai, India. Aluminium isopropoxide, aluminium sulphate, and so-
dium silicate were procured from Merck, India. SRL and Chemplast of
India supplied Cetyl trimethyl ammonium bromide (CTAB), Tetra
ethyl ammonium hydroxide (TEAOH) and Tetra ethyl ortho silicate
(TEOS) respectively.
2.2. Synthesis of catalysts
2.2.1. Synthesis of zeolite Hβ
Microporous Hβ was prepared using the method reported else-
where (Zhao et al., 2019). A molar ratio of 1:50, Aluminium and Silica
was maintained to synthesize a mixture using 27 mol of surface
directing agent TEAOH in aqueous media. TEOS and aluminium
isopropoxidewas used as silicon and aluminium source. The hydrother-
mal crystallization was done in an autoclave for three days at 140 °C.
The slurry product after filtration was dried in air oven at 100 °C and
the sodium ion exchange was performed using 1 M sol of NH4NO3.
The calcination of the dried mixture at 550 °C for 5–6 h yields Hβ.
2.3. Synthesis of Aluminium incoroporated MCM-41
In this work, Silicon and aluminium source for mesoporous material
was provided by SodiumO- silicate and aluminium sulphate (Al2(So4)3)
respectively. Chen et al. prepared AlMCM-41 catalyst using CTAB as
R. Ganesan, S. Subramaniam, R. Paramasivam et al. Science of the Total Environment 757 (2021) 143781
structure directing agent from natural Perlite. Similarly, in this method
CTAB was used as framework guiding agent. Sodium silicate (X g) was
dissolved in 150 to 200mLofwater and varied quantities of aqueous so-
lution of aluminium sulphate was stirred separately (Chen et al., 2019).
The thick white solution of aluminium sulphate was dropped slowly
through a burette to the silicate in the beaker with vigorous mixing
for 1 h. 4 N H2SO4 was added to maintain a pH of 11.6 in the mixture.
The gel obtained was stirred for 11/2 h. In the next step, upon continu-
ous stirring for 2 h the gel mixture and X g of CTAB solution was com-
bined. Hydrothermal crystallization of the resultant mixture was done
in an autoclave at 160 °C for 17 h. The slurry was filtered and air
dried. Muffle furnace was used to calcinate the product with the flow
of N2 (g) followed by air for 5 h at 550 °C.
2.4. Catalyst characterization
TPD analysis was carried out for determining acidity of the catalysts
(Micrometrics, ChemiSoft TPx 2750 V1.02 Unit 1 fitted with TCD). Pre-
treatment of catalyst in Helium atmosphere at a flow rate of 20 mL−1
was performed over certain mass of catalyst at 600 °C/1 h and cooled
to room temperature. The catalysts were cooled to reach room temper-
ature and ammonia/He ratio of (10/90 V/V) was introduced at a flow
rate of 20 mL−1 for 1 h. The desorption of physisorbed ammonia was
done by raising the temperature to 70 °C at a heating rate of 15 °C/
min. Ammonia adsorbed catalyst was then desorbed from 30 °C to
700 °C at 10 °C/min in the TPD setup attached to thermal conductivity
detector. Surface area analysis of the synthesized catalyst was quanti-
fied using Brunauer–Emmett–Teller method (Micromertics Pulse
Fig. 1. Schematic represent
3
Chemisorb 2700). At a controlled mixture of Nitrogen and Helium
ratio, a temperature of (−196 °C) is maintained where nitrogen exist
as liquid phase. At first nitrogen was passed through the catalysts sur-
face at 200 to 2500 °C to clean the pores using Micromeritics Desorb
2300A. Diffraction of catalysts was recorded using X-ray diffractometer
(Seifert model JSO DEBYEEFLEX 2002 equipment) with a Ni filter. The
wavelength of Cu Kα radiation was 0.1514 nm and the scanning was
set at 2θ range of 0.5°–70° and a step size to time ratio of 0.01°:2.3 s.
The % of major elements like Silicon and Aluminium were analyzed
using an ICP spectrometer (IOC OES, Thermo Fischer Scientific).
2.5. Cracking of oils in a fixed bed reactor
Hβ catalyst was used to optimize the operating conditions of crack-
ing reaction in the cracking unit made of quartz (1:2 width/height) to-
wards cracking of used mustard oil. The catalyst (Hβ as well as
AlMCM-41) was first pelletized to get the thickness around 5 mm and
then packed into the reactor along with quartz wool. Pelletized
AlMCM-41 catalysts were investigated to convert bio originated oils
under this optimized condition. The schematic representation of crack-
ing unit is shown in Fig. 1. Vapourization of vegetable oil was endured
by injecting it into the reactor placed in the temperature controlled
tubular furnace. A doublewalled Leibig condensermaintained at 0 °C at-
tached to the end of the reactor collected the condensed cracked prod-
ucts and the receiver placed in the ice mixture collected the liquid
hydrocarbons and the gaseous products were collected in a balloon. Ac-
etone wash was doneto the catalyst and the catalyst was reused after
calcination. The amount of coke deposited was estimated by the
ation of cracking unit.
Table 1
Fatty acid profile of vegetable oils employed in the study.
Fatty acid composition (%)
SAP, iodine and FFA value
Castor oil Neem oil Pongamia oil Coconut oil Mustard oil
Lauric acid (C12H24O2) C12:O – – – 49.0 –
Linoleic acid (C18H32O2) C18:2 w-6 – – – 1.8 25.4
Myristic acid (C14H28O2) C14:0 – – – 17.5 –
Palmitic acid (C16H32O2) C16:0 <1 16.0 8.9 9.0 4.3
Palmitoleic acid (C14H28O2) C16:1 – – – – –
Stearic acid (C18H36O2) C18:0 <1 24 8.2 3.0 2.8
Oleic acid (C18H34O2) C12:0 5 54 65.8 5.0 39
Linolenic acid (C18H30O2) C18:3 – – – – 11.3
Arachidic acid (C20H40O2) C20:O – – – – 11.1
Erucic (C22H42O2) C22:1 – – – – 11.4
Ricinoleic acid (C18H34O3) C18:1 85–95 – – – –
R. Ganesan, S. Subramaniam, R. Paramasivam et al. Science of the Total Environment 757 (2021) 143781
difference between the catalyst after cracking and unspent catalyst. The
liquid and gaseous products collected for every 1 h was analyzed by GC
instrument (Shimadzu QP 5000 GC 17A) furnished with the flame
ionization detector fitted with hydrocarbon greased column of two-
meter length and 0.125 diameter. The uncondensable products (lower
than C3 hydrocarbons) was traced using an ethylvinylbenzene-
divinylbenzene polymer column. The standard used for comparing %
CBL present in liquid sample was n-heptane and the area occupied by
injected liquid sample was compared with the area of n- heptane. The
set of carbon compounds were detected in the product by comparison
of their retention timeswith that of available standards. Themathemat-
ical equation listed below calculates the conversion of oil and the % of
liquid fraction. The selectiveness of the catalysts in producing gasoline,
kerosene and diesel hydrocarbon ranges were found using these
formulae.
%Conversion of vegetable oil
¼ Mass of CBLþ Gaseous productsþ Carbonaceous substanceþ aqueous phaseð Þ
Mass of oil fed into catalytic system
ð1Þ
%Yield of CBL or gaseous products ¼ Mass of CBL or gaseous productsð Þ
Mass of oil fed into catalytic system
ð2Þ
%BG;BK and ¼ Mass of BG;BK ad BD range of hydrocarbons present in CBL
Mass of CBL
ð3Þ
2.6. Fatty acid profile of vegetable oils employed in the study and thermo-
chemical analysis of CBL
The fatty acid profile of the vegetable oils cracked in the present re-
searchwork using GC (Agilent 6890-HP5975model) is given in Table 1.
Calorific value, viscosity and flash point are the primary thermo-
chemical parameters to analyze a fuel. The CBL was subjected to the
mentioned analysis and the details regarding the instruments used for
the analysis is provided in Table 2. CBL was tested in a single cylinder
compression engine at a compression ratio of 17.5:1 and 5 KW power.
Table 2
The various instruments used and standard methods adopted for the analysis of fuels.
S. no Parameter Unit Standard meth
1. Calorific value Cal/g ASTM D 240
2. Flash point °C ASTM D 92
3. Viscosity @ 40 °C mm2/s ASTM D 445
4
3. Results and discussion
3.1. Characterization report of catalysts
The patterns of X-ray diffraction of the catalysts are shown in Fig. 2.
XRD peaks of Hβ exhibit strong peaks in the 2θ range of 20°–30° which
resembles the patterns by Sansuk and Subsadsana (2019). The
sharpness of the XRD peaks indicates high crystalline nature of the syn-
thesized microporous materials. The XRD peaks of aluminium incorpo-
rated MCM-41 with varied incorporations exhibit three different peaks
equivalent to the planes 100, 110 and 200 at the 2θ values between 1.8°
and 5° which confirm the mesoporous nature of the materials (Ramesh
et al., 2020). From the Bragg's equation (nλ = 2dsinθ), the d spacing
values were calculated, and equation a0 = 2d100/1.732 is used to deter-
mine the lattice constants for all the AlMCM-41 catalysts (Table 3).
These characteristic peaks indicate the formation of mesoporous mate-
rials. With increase in addition of aluminium content, the peaks became
less intense, broader and moved to 2θ values of higher values as re-
ported (Chermahini and Nazeri, 2017). The 100 diffraction peaks broad-
ened and became less intense with decrease in Si/Al ratio whichmay be
due to the disturbance in the Si-O-Si bond resulting in distortion of long
range order ofmesoporous hexagonal framework. Such broadeningwas
also observed and reported (Sakmeche et al., 2020; Taheri et al., 2019).
The isomorphous substitution of Al3+with higher atomic radii of 53 pm
for Si4+ with atomic radii of 40 pm leads to the decrease in the d100
spacing value that corresponds to the shift of peak to higher 2θ values
(de Morais Araújo et al., 2017). With decrease in aluminium, d100
value changed from 3.58 nm to 4.20 nm in AlMCM-41 catalysts. Since
the 2θ value decreased with the increase in Si/Al ratio, it is obvious
that d100 value will increase (La-Salvia et al., 2017). The presence of
higher aluminium resulted in low crystallinity of AlMCM-41 (Locus
et al., 2016). The bond length of Si-O-Si in silicate framework
(164.6 pm) is extended by 5.7%which could be accounted for the incor-
poration of aluminium in Si-O-Si lattice. Silicon and aluminium contents
analyzed by ICP and surface characteristics analyzed by BET surface area
analyzer are given in Table 1.
The Si/Al ratios of AlMCM-41 matched with the estimated values
which are placed in brackets. The data projects the incomplete substitu-
tion of aluminium source into the Silicon cluster and this may be a rea-
son for marginal increase in the Si/Al value. Specific surface areas of
AlMCM-41 was higher than Hβ (635 m2/g) because of the large pores
of mesoporous catalyst. The higher siliceous content in the material
displayed considerable surface area while doping with Aluminium
od followed Model and make of the instrument
Bomb calorimeter, RSB-64A, Rajdhani, India.
Abel apparatus, RT 01, Royal, India.
Cannon-fensky viscometer, 9721-B59, Cole-parmer, India.
https://en.wikipedia.org/wiki/Ricinoleic_acid
https://en.wikipedia.org/wiki/Ricinoleic_acid
Fig. 2. XRD pattern of (a) Hβ; (b) AlMCM-41 with different Si/Al ratios.
R. Ganesan, S. Subramaniam, R. Paramasivam et al. Science of the Total Environment 757 (2021) 143781
reduced the area. Research articles also support the similar results and
the influence of Aluminium in the catalyst could be understood well
(Sterczyńska et al., 2017; Kadi et al., 2019). In the series of MCM41 pre-
pared with varying Si/Al ratio, the maximum surface area of 1023 m2/g
was possessed by MCM-41 (Si/Al = 101). The distortion of structure
with increase in aluminium content into the lattice leads to lower sur-
face area. From the BET isotherms using N2 as adsorbate one can under-
stand the type of porosity present in the synthesized catalysts. The four
stages of adsorption namely (i) slow adsorption of N2, (ii) a sudden
surge, (iii) a plateau and (iv) a sudden uptake of N2 are characteristics
of mesoporousmaterials and can be explained due to (i) monolayer ad-
sorption, (ii) multilayer adsorption on the pore walls, (iii) capillary con-
densation and (iii) only multilayer adsorption and (iv) increase in
Table 3
Characterization details of catalyst.
Catalyst Si/Al ratio Unit Cella0b (nm) BET surface area (m2/g)
Hβ (25) 27 6.6 635
AlMCM-41 (25) 27 3.58 950.8
AlMCM-41 (50) 52 4.09 976.6
AlMCM-41 (75) 75.5 4.20 1018
AlMCM-41 (100) 101 4.20 1023
5
adsorption due to the increase in aluminium content respectively. BET
isotherms were constructed using BET analyzer for all the Al-MCM-41
materials of different Si/Al ratios. The corresponding isotherms are pre-
sented in Fig. 3. The isotherms clearly indicate type IV adsorption iso-
therm confirming the mesoporosity of the material (Gu et al., 2013).
The small hysteresis loop showed by AlMCM-41 materials agrees with
the IUPAC classification of AlMCM-41 materials. TPD profiles give both
the number and distribution of acid sites which are expected to increase
with increase in aluminium content (Gutta et al., 2019).In the case of
mesoporousmaterials (AlMCM-41), the acidity increasedwith decrease
in Si/Al ratio. Although the TPDprofile gives only one peak, it is not sym-
metrical in nature which implies that the signal obtainedmay be due to
the desorption from two different acid sites namely weak acid sites and
Pore volume (cm3/g) Average pore size (nm) Total acidity (mL/g)
0.27 2.0 3.50
0.94 2.5 3.80
0.95 2.53 3.71
0.95 2.63 3.55
0.96 2.64 3.26
Fig. 3. N2 adsorption isotherm of AlMCM-41 (27).
R. Ganesan, S. Subramaniam, R. Paramasivam et al. Science of the Total Environment 757 (2021) 143781
moderate acid sites. In order to estimate these different types of acidi-
ties, the TPD profile of AlMCM-41 (27) has been deconvoluted and
shown in Fig. 4. The lower temperature peak indicates the availability
of Lewis acidic sites, and peaks centered around 280 °Cmay be presence
of dual acidic centers (Lewis and Bronsted). In the SEM picture, all the
particles look alike and therefore homogeneity of the material is agree-
able (Fig. 5a). The uniform outlook of the catalyst in SEM picture should
be due to even substitution of the aluminium atoms in the Si\\O net-
work. Boldrini et al. (2019) also obtained homogeneous pattern for
Fig. 4. Deconvoluted pea
6
AlMCM-41materials. The TEM image of thismaterial shows theuniform
hexagonal pore geometrywhich is characteristic of AlMCM-41material.
The unidirectional and ordered structure is seen in the TEM image. The
TEM image (Fig. 5c) of the synthesized AlMCM-41 is comparable with
the images found in literature (Wang et al., 2019). The interplanar dis-
tance corresponding to its [100] plane as calculated from the fringes
pattern is 4 nm, confirming the value obtained fromXRD. The SAED pat-
tern (Fig. 5b) shows the pattern characteristic of non-crystalline
material.
k of AlMCM-41 (27).
Fig. 5. a) SEM picture of synthesized AlMCM-41 (27) catalyst; (b) SAED pattern of AlMCM-41 b) TEM photograph of hexagonal AlMCM-41 (27).
Fig. 6. Catalytic activity of catalysts in cracking of mustard oil (Reaction conditions:
temperature- 400 °C, WHSV – 4.6 h−1 and time of reaction – 1 h).
R. Ganesan, S. Subramaniam, R. Paramasivam et al. Science of the Total Environment 757 (2021) 143781
3.2. Efficiency of mesoporous catalysts in the conversion of usedmustard oil
In the case of catalytic cracking, temperature, Weight Hourly Space
Velocity (WHSV) and time of collection of product are the deciding fac-
tor for the better yield of bioliquid and gasoline fraction. In our earlier
research, optimization studies were attempted in cracking of jatropha
oil using Hβ catalyst and the same optimization conditions were
opted for the cracking of mustard oil (Ramya et al., 2015). The reactions
were performed at a temperature of 400 °C, 4.6 h−1 WHSV and the
bioliquid product was collected in every 1st h of reaction with the dis-
cretion of product collected in first 5 min. Performance of the catalysts
towards cracking of used mustard oil is shown in Fig. 6. The data
shows that the catalysts contributed to the better conversion of the veg-
etable oils into bioliquid. In comparison with Hβ, mesoporous catalysts
have surpassed owing to its better activity which may be justified by
their bigger pore size that facilitates the passage of fatty acid molecules.
The microporous catalyst produced 25% of liquid fuels by converting
55% of mustard oil. As compared to Hβ, a nearly two fold increase
could be observed in the conversion of mustard oil into useful products.
AlMCM-41 catalyst with Si/Al ratio of 27 drastically converted 75% of oil
into 50% of bio liquids. This also faced a decreasing trend with the in-
crease in Si/Al ratios. AlMCM-41 (52) was the successor in the series
with good catalytic activity with 70% conversion and 40% bio liquid
yield. Besides, AlMCM-41 (101) with the highest silicon content was
the lowest reacting mesoporous catalyst with similar conversion rate
of Hβ. However, the yield of bio liquid component (35%) was fairly
higher than that of Hβ. It has to be noted that SBA-15 yet another
7
mesoporous catalyst also produced limited amount of gas fractions
(<C4)whichmaybe due to themild acidic nature and larger pore diam-
eter. The % yield of gaseous hydrocarbons increased along the decrease
Table 4
Selectivity pattern of AlMCM-41 (27) in cracking mustard oil.
Catalyst BG BK BD
Hβ 35 40 25
AlMCM-41 (27) 55 28.5 16.5
AlMCM-41 (52) 50 30.3 19.7
AlMCM-41 (75) 45.6 33.5 20.9
AlMCM-41 (101) 41.3 35.8 22.9
Reaction conditions: temperature - 400 °C, WHSV – 4.6 h−1 and time of reaction – 1 h.
Table 6
Comparison of fuel properties of CBL vs Castor biodiesel.
Parameters CBL Castor biodiesel
Flash point (°C) 28 120
Viscosity (mm2/s) 8.6 2
Calorific value (Cal/g) 10,000 9500
Sulphur emissions (%) 0.001 0.01
NOX emissions (%) 0.22 0.5
CO emissions (%) 2.5 2.7
R. Ganesan, S. Subramaniam, R. Paramasivam et al. Science of the Total Environment 757 (2021) 143781
in Si/Al ratio in AlSBA-15 (Socci et al., 2019). This may be due to rise in
acidity on increasing the incorporation of aluminium ions (Al3+) in the
siliceous lattice of the catalyst (Ortiz-Bravo et al., 2020). The higher
acidic nature of the catalyst caused severe cracking leading to dramati-
cally high yield of gaseous fragments (Makertihartha et al., 2020).
Though the good rate of conversion (%) and distribution of bioliquid is
important, product specificity towards BG product has equal signifi-
cance. AlMCM-41 (27) selectively cracked mustard oil into BG fraction
of about 55% and the latter showed comparatively low yields as given
in Table 4. A substantial drop in selectivity of BGwith increase inmiddle
fractions (BK and BD) was observed. This could be probably due to the
low acidic nature of the catalysts with higher content of silicon com-
pared to aluminium (Ganesan et al., 2019). Singh et al. (Singh et al.,
2019) cracked linoleic acid with microporous catalysts and observed
that gasoline fraction was highly dependent on the acidic sites of the
catalysts.
3.3. Catalytic efficiency of AlMCM-41(27) in cracking of castor, neem, fresh
and used coconut oil
AlMCM-41 catalyst (Si/Al = 27) beckoned to be better cracker for
other vegetable oils used in the study with the higher % yield of BG deliv-
ered in cracking of used mustard oil. Investigation of this catalyst in the
cracking is other oil is given in Table 5 and it records the conversion,
yield of bioliquid and selectivity of BGandmiddle distillates. Castor oil, ba-
sicallywith 90% of ricinoleic acid; amonounsaturated fatty acidwas effec-
tively converted (100%) by the synthesized catalyst. The cracked oil
yielded 85% castor bioliquid (CBL)with highest BG of 70%. The conversion
of neemoil (65%)was the next highest compared to other oils. Used coco-
nut oil was the least converted (45%) and this may be due to their high
free fatty acids by repeated usage. Since the vegetable oils have distinct
proportions of fatty acids, the result is incomparable with each other.
The minimum % of BG fraction (40%) was obtained from used coconut
oil. Nickel loaded MCM-41 catalyst was reported in cracking of camelina
oil into hydrocarbon fuels at 450 °C (Xu et al., 2020).
3.4. Thermo chemical investigations of the CBL produced from castor oil
Table 6 gives the fuel characteristics and the values of castor biodie-
sel are given for comparison purpose. ASTM and ISO standards areman-
datory to understand the characteristics of the alternative fuel.
Kinematic viscosity of biodiesel produced from castor oil proposed by
Table 5
Cracking efficiency of AlMCM-41 (27) in cracking castor, neem, fresh and used coconut oil.
Vegetable
oil
Conversion
(%)
Bioliquid
(%)
Selectivity
%
BG
Selectivity
%
BK + BD
Gaseous
products
(%)
Castor 98 85 70 29 10
Neem 65 30 60 40 32
Pongamia 62 25 52 48 35
Fresh
coconut
60 35 45 55 21
Used
coconut
45 25 40 58 15
Reaction conditions: temperature - 400 °C, WHSV – 4.6 h−1 and time of reaction – 1 h.
8
da Silva et al. (2013) was four times higher than the ASTM specificationof biodiesel (2.4 mm2/s) (Musa et al., 2018). The viscosity of BG pro-
duced from castor oil analyzed by ASTM D 445 was found to be
2 mm2/s and was in the permissible limit. The fuel economy is propor-
tional to the viscosity and running the enginewith higher dense fuel de-
creases the fuel economy. The engines running with lower calorific
value fuels witness more exhaust comprising air pollutants due to in-
complete combustion of fuels. But, the calorific value of the synthesized
BGwas 10,000 Cal/g according to ASTMD240whichwas comparable to
commercial gasoline (10,604 Cal/g). The indispensable fuel property
important for safe handling of fuel, transportation and storing for long
time is based on the flash point of the fuel. The flash point of castor oil
biodiesel as 120 °C which was higher than the ASTM D 92 standards
(da Silva et al., 2013). The Flash point of the castor derived BG was
28 °C whereas the ASTM standard value for biodiesel is 93 °C which
guarantees the use of such fuel in modern day engines. The fatty acid
profile shows that the oil is rich in their characteristic monosaturated
or unsaturated fatty acids. Among the oils, castor oil has shown excel-
lent yield. The fuel Produced from castor exhibited low viscosity and
low pour point which enhances its ability to be used in colder regions.
The presence of oleic acid generally decreases the clogging effect in en-
gines formed by the fuel working at low temperatures. The sulphur
emitted during the toxic gas emission testingwas less than 0.001%. Sim-
ilarly, low emission of sulphur from biodiesel prepared from castor oil
was reported by Keera et al. (2018). The CO emission and NOX emission
index were similar to that of fossil fuels and the temperature inside the
engine cylinder may have led to the observation.
4. Conclusion
Hβ and AlMCM-41 catalysts were synthesized and characterization
results confirmed the formation of catalysts. In the present study, meso-
porous catalyst AlMCM-41 (27) converted 75% of used mustard oil to
48% bioliquid with 67% selectivity towards BG. In the cracking of other
non-edible vegetable oils, AlMCM-41 (27) converted 98% of castor oil
into CBL with 85% of BG. The catalysts showed good activity in cracking
the other oils with higher % of gasoline fraction. The calorific value and
flash point of CBL showed significant values and it distinguished them
from other alternative fuels owing to their ready usage in the engine.
The emission data reveals traces of toxic emissions such as NOX and
SOx and hence promises its utility in the future.
CRediT authorship contribution statement
Ramya Ganesan: Conceptualization, Methodology, Writing - original
draft. Shanthi Subramaniam: Investigation, Writing - original draft.
Ravichandran Paramasivam: Writing - review & editing. Jamal S.M.
Sabir:Writing - review& editing. J.S. Femilda Josephin:Writing - review
& editing. Kathirvel Brindhadevi: Supervision, Project administration.
Arivalagan Pugazhendhi: Supervision, Project administration.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
R. Ganesan, S. Subramaniam, R. Paramasivam et al. Science of the Total Environment 757 (2021) 143781
Acknowledgments
This project was funded by The Deanship of Scientific Research
(DSR) at King Abdulaziz University, Jeddah, Saudi Arabia. Under grant
number (FP-40- 42).
References
Acharya, N., Nanda, P., Panda, S., Acharya, S., 2019. A comparative study of stability char-
acteristics of mahua and jatropha biodiesel and their blends. J. King Saud Univ. Eng.
Sci. 31 (2), 184–190.
Adepoju, T., 2020. Optimization processes of biodiesel production from pig and neem
(Azadirachta indica a. Juss) seeds blend oil using alternative catalysts fromwaste bio-
mass. Ind. Crop. Prod. 149, 112334.
Akah, A., Williams, J., Ghrami, M., 2019. An overview of light olefins production via steam
enhanced catalytic cracking. Catal. Surv. Jpn. 1–12.
Ambat, I., Srivastava, V., Sillanpää, M., 2018. Recent advancement in biodiesel production
methodologies using various feedstock: a review. Renew. Sust. Energ. Rev. 90,
356–369.
Banu, J.R., Sharmila, V.G., Ushani, U., Amudha, V., Kumar, G., 2020. Impervious and influ-
ence in the liquid fuel production from municipal plastic waste through thermo-
chemical biomass conversion technologies-a review. Sci. Total Environ. 718, 137287.
Boldrini, D.E., Angeletti, S., Cervellini, P.M., Reinoso, D.M., 2019. Highly ordered mesopo-
rous Al-MCM-41 synthesis through valorization of natural sediment. ACS Sustain.
Chem. Eng. 7 (5), 4684–4691.
Cao, X., Li, L., Shitao, Y., Liu, S., Hailong, Y., Qiong, W., et al., 2019. Catalytic conversion of
waste cooking oils for the production of liquid hydrocarbon biofuels using in-situ
coating metal oxide on SBA-15 as heterogeneous catalyst. J. Anal. Appl. Pyrolysis
138, 137–144.
Chen, R.-X., Wang, W.-C., 2019. The production of renewable aviation fuel from waste
cooking oil. Part I: bio-alkane conversion through hydro-processing of oil. Renew. En-
ergy 135, 819–835.
Chen, H., Fu, S., Fu, L., Yang, H., Chen, D., 2019. Simple synthesis and characterization of
hexagonal and ordered Al–MCM–41 from natural perlite. Minerals 9 (5), 264.
Chermahini, A.N., Nazeri, M., 2017. Esterification of the levulinic acid with n-butyl and
isobutyl alcohols over aluminum-containing MCM-41. Fuel Process. Technol. 167,
442–450.
da Silva, NdL, Santander, C.M.G., Rueda, SmGm,Wolf Maciel, M.R., M. Filho, R., 2013. Char-
acterization of blend properties of castor biodiesel and bioethanol. Ind. Eng. Chem.
Res. 52 (44), 15504–15508.
de Morais Araújo, A.M., de Oliveira Lima, R., Gondim, A.D., Diniz, J., Di Souza, L., de Araujo,
A.S., 2017. Thermal and catalytic pyrolysis of sunflower oil using AlMCM-41. Renew.
Energy 101, 900–906.
Dhanya, B., Mishra, A., Chandel, A.K., Verma, M.L., 2020. Development of sustainable ap-
proaches for converting the organic waste to bioenergy. Sci. Total Environ. 723,
138109.
Dorado, M.P., Ballesteros, E., López, F.J., Mittelbach, M., 2004. Optimization of alkali-
catalyzed transesterification of Brassica C arinata oil for biodiesel production. Energy
Fuel 18 (1), 77–83.
Ganesan, R., Thiripuranthagan, S., Subba, S., 2019. Synthesis and characterization of core-
shell modeled AlMCM-48/HZSM-5 composite catalyst and studies on its catalytic ac-
tivity in cracking of pongamia oil into bio liquid products. Bioenergy Res. 12 (2),
388–399.
Ganesan, R., Manigandan, S., Samuel, M.S., Shanmuganathan, R., Brindhadevi, K., Chi,
N.T.L., et al., 2020. A review on prospective production of biofuel from microalgae.
Biotechnol. Rep. e00509.
Goh, B.H.H., Ong, H.C., Cheah, M.Y., Chen, W.-H., Yu, K.L., Mahlia, T.M.I., 2019. Sustainabil-
ity of direct biodiesel synthesis from microalgae biomass: a critical review. Renew.
Sust. Energ. Rev. 107, 59–74.
Gu, S.H., Nicolas, V., Lalis, A., Sathirapongsasuti, N., Yanagihara, R., 2013. Complete ge-
nome sequence and molecular phylogeny of a newfound hantavirus harbored by
the Doucet’s musk shrew (Crocidura douceti) in Guinea. Infect. Genet. Evol. 20,
118–123.
Gutta, N., Velisoju, V.K., Tardio, J., Patel, J., Satyanarayana, L., Sarma, A.V., et al., 2019. CH4
cracking over the Cu–Ni/Al-MCM-41 catalyst for the simultaneous production of H2
and highly ordered graphitic carbon nanofibers. Energy Fuel 33 (12), 12656–12665.
Han, W., Liu, Y., Xu, X., Huang, J., He, H., Chen, L., et al., 2020. Bioethanol production from
waste hamburger by enzymatic hydrolysis and fermentation. J. Clean. Prod. 264,
121658. https://doi.org/10.1016/j.jclepro.2020.121658.
Javed, S.A., Zhu, B., Liu, S., 2020. Forecast of biofuel production and consumption in top
CO2 emitting countries using a novel grey model. J. Clean. Prod. 276, 123997.
Junne, S., Kabisch, J., 2017. Fueling the future with biomass: processes and pathways for a
sustainable supply of hydrocarbon fuels andbiogas. Eng. Life Sci. 17 (1), 14–26.
Kadi, M.W., Hameed, A., Mohamed, R., Ismail, I.M., Alangari, Y., Cheng, H.-M., 2019. The ef-
fect of Pt nanoparticles distribution on the removal of cyanide by TiO2 coated Al-
MCM-41 in blue light exposure. Arab. J. Chem. 12 (7), 957–965.
Keera, S., El Sabagh, S., Taman, A., 2018. Castor oil biodiesel production and optimization.
Egypt. J. Pet. 27 (4), 979–984.
Kumar, P., Sharma, M.P., Dwivedi, G., 2016. Impact of ternary blends of biodiesel on diesel
engine performance. Egypt. J. Pet. 25 (2), 255–261.
Kumari, D., Singh, R., 2018. Pretreatment of lignocellulosic wastes for biofuel production:
a critical review. Renew. Sust. Energ. Rev. 90, 877–891.
9
La-Salvia, N., Lovón-Quintana, J.J., Lovón, A.S.P., Valença, G.P., 2017. Influence of aluminum
addition in the framework of MCM-41 mesoporous molecular sieve synthesized by
non-hydrothermal method in an alkali-free system. Mater. Res. 20 (6), 1461–1469.
Locus, R., Verboekend, D., Zhong, R., Houthoofd, K., Jaumann, T., Oswald, S., et al., 2016.
Enhanced acidity and accessibility in Al-MCM-41 through aluminum activation.
Chem. Mater. 28 (21), 7731–7743.
Machacon, H.T., Shiga, S., Karasawa, T., Nakamura, H., 2001. Performance and emission
characteristics of a diesel engine fueled with coconut oil–diesel fuel blend. Biomass
Bioenergy 20 (1), 63–69.
Makertihartha, I.G.B., Fitradi, R.B., Ramadhani, A.R., Laniwati, M., Muraza, O., 2020.
Biogasoline production from palm oil: optimization of catalytic cracking parameters.
Arab. J. Sci. Eng. 1–10.
Mishra, R.K., Mohanty, K., 2018. Thermocatalytic conversion of non-edible Neem seeds to-
wards clean fuel and chemicals. J. Anal. Appl. Pyrolysis 134, 83–92.
Mitrović, P.M., Stamenković, O.S., Banković-Ilić, I., Djalović, I.G., Nježić, Z.B., Farooq, M., et
al., 2020. White mustard (Sinapis alba L.) oil in biodiesel production: a review. Front.
Plant Sci. 11, 299.
Mona, S., Kumar, S.S., Kumar, V., Parveen, K., Saini, N., Deepak, B., et al., 2020. Green tech-
nology for sustainable biohydrogen production (waste to energy): a review. Sci. Total
Environ. 728, 138481. https://doi.org/10.1016/j.scitotenv.2020.138481.
Musa, M.L., Mat, R., Abdullah, T.A.T., 2018. Optimised biofuel production via catalytic
cracking of residual palm oil recovered from spent bleaching earth (SBE) over Ni/
HZSM-5 zeolite. J. Adv. Res. Fluid Mech. Therm. Sci. 51 (2), 108–123.
Nagaraj, S.K., Ponnusamy, P., Nagarajan, B.M., 2020. Evaluation of emission in a diesel en-
gine with neem and pongamia (Karanja) mixed bio oil using 3-hole and 4-hole noz-
zle. Mater. Today Proc. https://doi.org/10.1016/j.matpr.2020.07.496.
Niculescu, R., Clenci, A., Iorga-Siman, V., 2019. Review on the use of diesel–biodiesel–alco-
hol blends in compression ignition engines. Energies 12 (7), 1194.
Orjuela, A., Clark, J., 2020. Green chemicals from used cooking oils: trends, challenges and
opportunities. Curr. Opin. Green Sustain. Chem. 26, 100369. https://doi.org/10.1016/j.
cogsc.2020.100369.
Ortiz-Bravo, C.A., Zandonai, C.H., Olsen-Scaliante, M.H.N., Fernandes, N.R.C., 2020. Produc-
ing gasoline-like hydrocarbons by cracking crude soybean oil: tuning the NaZSM-5
zeolite’s acidity for increasing the catalyst lifetime. Braz. J. Chem. Eng. 1–11.
Pechout, M., Kotek, M., Jindra, P., Macoun, D., Hart, J., Vojtisek-Lom, M., 2019. Comparison
of hydrogenated vegetable oil and biodiesel effects on combustion, unregulated and
regulated gaseous pollutants and DPF regeneration procedure in a Euro6 car. Sci.
Total Environ. 696, 133748.
Perego, C., Bosetti, A., Ricci, M., Millini, R., 2017. Zeolite materials for biomass conversion
to biofuel. Energy Fuel 31 (8), 7721–7733.
Pollitt, K.J.G., Chhan, D., Rais, K., Pan, K., Wallace, J.S., 2019. Biodiesel fuels: a greener die-
sel? A review from a health perspective. Sci. Total Environ. 688, 1036–1055.
Ramesh, A., Tamizhdurai, P., Krishnan, P.S., Ponnusamy, V.K., Sakthinathan, S., Shanthi, K.,
2020. Catalytic transformation of non-edible oils to biofuels through
hydrodeoxygenation using Mo-Ni/mesoporous alumina-silica catalysts. Fuel 262,
116494.
Ramírez, V., Martí-Herrero, J., Romero,M., Rivadeneira, D., 2019. Energy use of Jatropha oil
extraction wastes: pellets from biochar and Jatropha shell blends. J. Clean. Prod. 215,
1095–1102.
Ramya, G., Sivakumar, T., Arif, M., Ahmed, Z., 2015. Catalytic cracking using an Hβ catalyst
for the production of green fuel: optimization studies. Energ. Source Part A Recover.
Utilization Environ. Eff. 37 (7), 758–765.
Sadeek, S.A., Mohammed, E.A., Shaban, M., Abou Kana, M.T., Negm, N.A., 2020. Synthesis,
characterization and catalytic performances of activated carbon-doped transition
metals during biofuel production from waste cooking oils. J. Mol. Liq. 306, 112749.
https://doi.org/10.1016/j.molliq.2020.112749.
Sakmeche, M., Belhakem, A., Ghomari, S.A., Belgacem, L., 2020. Hydroconversion of nC 10
alkanes using functionalized AlMCM-41 as catalysts. React. Kinet. Mech. Catal. 129
(2), 975–990.
Sansuk, S., Subsadsana, M., 2019. Synthesis of 5-hydroxymethylfurfural from glucose
using H-Beta catalyst treated with phosphoric acid in one-pot biphasic solvent sys-
tem. Energ. Source Part A Recover. Utilization Environ. Eff. 41 (22), 2769–2777.
Singh, H.K.G., Yusup, S., Quitain, A.T., Kida, T., Sasaki, M., Cheah, K.W., et al., 2019. Produc-
tion of gasoline range hydrocarbons from catalytic cracking of linoleic acid over var-
ious acidic zeolite catalysts. Environ. Sci. Pollut. Res. 26 (33), 34039–34046.
Socci, J., Osatiashtiani, A., Kyriakou, G., Bridgwater, T., 2019. The catalytic cracking of ste-
rically challenging plastic feedstocks over high acid density Al-SBA-15 catalysts. Appl.
Catal. A Gen. 570, 218–227.
Soongprasit, K., Sricharoenchaikul, V., Atong, D., 2019. Pyrolysis of Millettia (Pongamia)
pinnata waste for bio-oil production using a fly ash derived ZSM-5 catalyst. J. Anal.
Appl. Pyrolysis 139, 239–249.
Sterczyńska, A., Deryło-Marczewska, A., Zienkiewicz-Strzałka, M., Śliwińska-Bartkowiak,
M., Domin, K., 2017. Surface properties of Al-functionalized mesoporous MCM-41
and the melting behavior of water in Al-MCM-41 nanopores. Langmuir 33 (42),
11203–11216.
Taheri, M., Ghiaci, M., Moheb, A., Shchukarev, A., 2019. Organic–inorganic hybrid of an-
chored dicationic ionic liquid on Al-MCM-41-phosphovanadomolybdate toward se-
lective oxidation of benzene to phenol. Appl. Organomet. Chem. 33 (8), e5012.
Wang, R., Lin, Z.X., Zhao, Y., Xu, X.D., Deng, Y.X., 2019. Synthesis and preparation of Al-
MCM-41 mesoporous materials using oil shale residue. Materials Science Forum.
vol. 944. Trans Tech Publ, pp. 1192–1198.
Wei, X., Xue, X., Wu, L., Yu, H., Liang, J., Sun, Y., 2020. High-grade bio-oil produced from
coconut shell: a comparative study of microwave reactor and core-shell catalyst. En-
ergy 212, 118692.
Wong, W.-Y., Lim, S., Pang, Y.-L., Shuit, S.-H., Chen, W.-H., Lee, K.-T., 2020. Synthesis of re-
newable heterogeneous acid catalyst from oil palm empty fruit bunch for glycerol-
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0005
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0005
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0005
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0010
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0010
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0010
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0015
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0015
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0020
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0020
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0020
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0025
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0025
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0025
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0030
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0030
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0030
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0035http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0035
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0035
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0035
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0040
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0040
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0040
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0045
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0045
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0050
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0050
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0050
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0055
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0055
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0055
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0060
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0060
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0065
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0065
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0065
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0070
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0070
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0070
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0075
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0075
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0075
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0075
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0080
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0080
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0085
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0085
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0085
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0090
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0090
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0090
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0090
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0095
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0095
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0095
https://doi.org/10.1016/j.jclepro.2020.121658
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0105
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0105
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0105
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0110
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0110
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0115
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0115
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0115
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0120
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0120
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0125
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0125
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0130
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0130
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0135
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0135
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0135
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0140
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0140
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0145
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0145
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0145
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0150
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0150
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0155
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0155
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0160
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0160
https://doi.org/10.1016/j.scitotenv.2020.138481
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0170
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0170
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0170
https://doi.org/10.1016/j.matpr.2020.07.496
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0180
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0180
https://doi.org/10.1016/j.cogsc.2020.100369
https://doi.org/10.1016/j.cogsc.2020.100369
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0190
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0190
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0190
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0195
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0195
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0195
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0195
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0200
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0200
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0205
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0205
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0210
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0210
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0210
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0215
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0215
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0215
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0220
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0220
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0220
https://doi.org/10.1016/j.molliq.2020.112749
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0230
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0230
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0230
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0235
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0235
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0235
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0240
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0240
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0240
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0245
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0245
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0245
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0250
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0250
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0250
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0255
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0255
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0255
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0260
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0260
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0260
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0265
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0265
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0265
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0270
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0270
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0270
R. Ganesan, S. Subramaniam, R. Paramasivam et al. Science of the Total Environment 757 (2021) 143781
free biodiesel production. Sci. Total Environ. 727, 138534. https://doi.org/10.1016/j.
scitotenv.2020.138534.
Wu, H., Zheng, J., Wang, G., 2019. Catalytic liquefaction of switchgrass in isobutanol/water
system for bio-oil development over bifunctional Ni-HPMo/Fe3O4@ Al-MCM-41 cat-
alysts. Renew. Energy 141, 96–106.
Xu, G., Jia, C., Shi, Z., Liang, R., Wu, C., Liu, H., et al., 2020. Enhanced catalytic conversion of
camelina oil to hydrocarbon fuels over Ni-MCM-41 catalysts. Sci. Adv. Mater. 12 (2),
304–311.
10
Yigezu, Z.D., Muthukumar, K., 2014. Catalytic cracking of vegetable oil with metal oxides
for biofuel production. Energy Convers. Manag. 84, 326–333.
Zhao, D., Wang, Y., Chu, W., Wang, X., Zhu, X., Li, X., et al., 2019. Direct synthesis of hollow
single-crystalline zeolite beta using a small organic lactam as a recyclable hollow-
directing agent. J. Mater. Chem. A 7 (17), 10795–10804.
https://doi.org/10.1016/j.scitotenv.2020.138534
https://doi.org/10.1016/j.scitotenv.2020.138534
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0280
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0280http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0280
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0285
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0285
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0285
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0290
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0290
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0295
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0295
http://refhub.elsevier.com/S0048-9697(20)37312-5/rf0295
	A study on biofuel produced by catalytic cracking of mustard and castor oil using porous Hβ and AlMCM-�41 catalysts
	1. Introduction
	2. Materials and methods
	2.1. Materials
	2.2. Synthesis of catalysts
	2.2.1. Synthesis of zeolite Hβ
	2.3. Synthesis of Aluminium incoroporated MCM-41
	2.4. Catalyst characterization
	2.5. Cracking of oils in a fixed bed reactor
	2.6. Fatty acid profile of vegetable oils employed in the study and thermo-chemical analysis of CBL
	3. Results and discussion
	3.1. Characterization report of catalysts
	3.2. Efficiency of mesoporous catalysts in the conversion of used mustard oil
	3.3. Catalytic efficiency of AlMCM-41(27) in cracking of castor, neem, fresh and used coconut oil
	3.4. Thermo chemical investigations of the CBL produced from castor oil
	4. Conclusion
	CRediT authorship contribution statement
	Declaration of competing interest
	Acknowledgments
	References