Fuel 259 (2020) 116262

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Fuel
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Review article

Sewage sludge to bio-fuel: A review on the sustainable approach of T

transforming sewage waste to alternative fuel
⁎
Akash Pratim Bora, Dipanshu Prakash Gupta, Krishna Sandilya Durbha
Department of Chemical Engineering, Indian Institute of Technology (Indian School of Mines), Dhanbad, Dhanbad 826004, Jharkhand, India

A R T I C LE I N FO A B S T R A C T

Keywords: Bio-fuels are gaining worldwide attention as an alternative fuel option replacing the usage of the mineral diesel
Bio-fuel derived from conventional fossil sources. However, the high cost attributed by the feedstock made it less
Sewage sludge competitive with the commercial diesel. A widespread research is going on worldwide for the production of fuels
Lipid extraction from renewable biomass replacing the currently used traditional sources. The high lipid-containing municipal
Transesterification
sewage sludge (MSS) can be considered as a potential feedstock owing to its low cost and abundant availability.
Heterogeneous catalyst
The lipids are transformed to biodiesel via transesterification or to bio-oil by pyrolysis. In this review paper, a
comprehensive discussion on the various aspects of bio-fuel production from sludge derived lipids along with the
key parameters affecting the process and its economics are presented. This review also emphasizes that future
studies should focus on the usage of modern process intensification techniques for more efficient production of
bio-fuel from renewable biomass.

1. Introduction delivery infrastructure, easier production methodology and economic

The world population is projected to reach 9.8 billion by 2050 and
further to 11.2 billion by 2100 [1]. With this increasing population, a
significant amount of fuel may be in demand in order to aid the energy
requirements in the coming years [2]. According to British Petroleum
(BP) statistical review of World Energy June 2017, global oil con-
sumption was observed to be 1.6 million barrels per day (Mb/d)
whereas the increase in global oil production was reported to be only
0.4 Mb/d. Additionally, with the global established oil reserves re-
ported to be 1707 billion barrels in 2016, that would be adequate for
50.6 years of oil production [3]. This dwindling in the energy genera-
tion is required to be addressed with the new sources which can
minimize the atmospheric greenhouse gas (GHG) emissions that are
largely contributed by fossil fuel and industrial processes [4], so as to
reduce the earth’s temperature.
The basic characteristics of the sustainable alternative fuels include
renewability, cost-effectiveness, efficient and less harmful nature to the
environment compared to the conventional fossil fuels [5,6]. In the past
few decades, several bio-fuels (bio-ethanol, bio-methanol, biodiesel,
dimethyl ether, bio-oil, biogas, bio-methane etc) have been developed,
biodiesel and bio-ethanol being the most widely used. The acceptance is
mainly because of their characteristics viz. slightly or without mod-
ifications necessitated in the existing engine hardware as well as fuel
viability [6]. But bio-ethanol is limited in its applicability as an additive
with gasoline for octane number enhancement to improve combustion
quality and engine performance. The thermal properties like calorific
value, cetane number and volatility properties are comparable with that
of the commercial diesel but there is a substantial difference in some
fuel properties like density, viscosity and oxygen content as well as the
requirement of stoichiometric fuel to air ratio. Although biodiesel has
approximately 10% lower heating value compared to mineral diesel,
owing to the higher specific gravity of the former it is ultimately at-
tributed to the 5% lower content of energy on the basis of unit volume.
The result is better thermal efficiency of the biodiesel-operated engine
when compared to the conventional diesel-operated engine [7,8].
Moreover, the elucidation of life cycle assessment data reveals that the
employment of biodiesel reduces the GHG emissions having a net en-
ergy ratio greater than 1.3 whereas it is only 0.19 in case of mineral
diesel [9,10]. Thus, biodiesel seems to be an attractive fuel omitting the
reliance on fossil fuels and is likely to reduce the global environmental
pollution along with the creation of job opportunity in rural sectors
[11].
Biodiesel is generally known as alkyl esters of fatty acid which can
be synthesised from the reaction of different lipid fractions with the
alcohol in aid of acid, base, solid or an enzyme catalyst [12–15]. The
major obstacle that lies in the path of commercializing the biodiesel

⁎
Corresponding author at: Room # 429, Fourth Floor, New Academic Complex, Department of Chemical Engineering, Indian Institute of Technology (Indian School
of Mines), Dhanbad, Dhanbad 826004, Jharkhand, India.
E-mail address: sandilya@iitism.ac.in (K.S. Durbha).

https://doi.org/10.1016/j.fuel.2019.116262
Received 20 May 2019; Received in revised form 12 August 2019; Accepted 21 September 2019
Available online 03 October 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
A.P. Bora, et al.
industry is the cost of its feedstock (mainly vegetable oils) which ac-
counts for more than 80% of the production cost [16–18]. In addition to
this, using vegetable oil for biodiesel production conflicts with the de-
mand for human consumption. Waste cooking oils being cheaper could
be an alternate feedstock but the challenge lies ahead as it affects the
consistency of the biodiesel produced due to its property variance and
requires additional cost for purification [10,15,18,19]. Researchers
now are looking into different non-edible oil sources like algae, ja-
tropha, karanja, or neem etc. as suitable alternatives for biodiesel
feedstock but it requires huge land for cultivation and their ease of
availability is a subject of concern [18,20–22]. Therefore, it is utmost
important to search for an alternate biodiesel feedstock that is readily
available and inexpensive.
Municipal sewage sludge (MSS) is gaining worldwide attention as it
is an abundant organic waste and contains a significant amount of li-
pids, which can make biodiesel production from sewage sludge lucra-
tive [23–25]. A wastewater treatment plant produces two main types of
sludge – a) primary sludge b) secondary sludge. The primary sludge is
the combination of solids materials and floating grease while the sec-
ondary sludge or activated sludge contains primarily microbial cells
and suspended solids. These two types of sludges can be collected from
the primary clarifier and secondary clarifiers respectively [17,25]. The
sewage sludge collected from the waste water treatment plant (WWTP)
is a heterogeneous mixture of different undigested organic materials,
microorganisms, oils, fats, inorganic materials and moisture [26]. The
schematic diagram of a typical WWTP is depicted in Fig. 1.
As illustrated graphically, before the sewage water is treated in
primary clarifier, it passes through the screening/grit removal chamber
where the rate of the sewage stream is monitored to settle down the
sand or grit. The primary sludge is collected from the primary clarifier
where it is disintegrated by mechanical means and sedimentation. It
contains mainly solids materials and floating grease and usually con-
tains more than 80% water. The effluent from the primary tank is
passed through the biological treatment processes where the microbial
breakdown of the organic matter is carried out via combination of the
anaerobic, anoxic and aerobic processes. After this treatment, the sec-
ondary or the activated sludge is collected from the secondary clarifier
which primarily consists of microbial cells and other suspended solids.
The blend of the thickened primary and secondary sludge is further
processed and stabilized in the anaerobic digester and the resultant
digested sludge is dehydrated with the help of centrifugation and finally
disposed off [27].
The management of sewage is a worldwide problem. Owing to the
Fig. 1. The schematic of a typical waste water treatment plant.
2
Fuel 259 (2020) 116262
increase in population and rapid industrialisation there is a growth in
the number of WWTPs. As a result, the amount of sewage sludge pro-
duced from the WWTPs increased drastically in recent decades and
thereby causing the detrimental effect on the environment. It is re-
ported that the annual growth of sludge was near about 13% in China in
a span of 9 years from 2007 and expected to reach around 60 million
tons in 2020 [28,29]. It was reported that the European Union alone is
generating around 50 million tons of sewage sludge annually while in
the United States the figure is 40 million tons [30,31]. The recent cost
analysis data estimated that 50 percent of the total operating cost ac-
counts for the sewage sludge management [32,33]. Previously many
techniques have been employed to manage the sewage sludge such as
incineration, ocean disposal, landfilling and agricultural usage. But
these processes had numerous drawbacks and environmental hazards.
In order to protect the marine ecology ocean disposal was prohibited by
the London Convention 97 protocol [34]. Moreover the presence of
heavy metals, organic pollutants, pathogens and other trace elements
confines the sludge to be used as fertilizers in agriculture [35]. Corre-
spondingly, due to the scarcity of land resources and prospective en-
vironmental damage, the landfilling of sludge is protected under new
legislations and regulations [36–38]. Thus, utilising sludge as the lipid
feedstock for biodiesel production makes it an alternative and sus-
tainable approach towards sludge management and disposal challenges.
Lipids are organic fatty acids or their derivatives consisting of gly-
cerides, free fatty acids, phospholipids, sphingo lipids etc. [39]. The
sewage sludge contains a significant amount of lipid fractions. The
presence of lipids in sewage sludge could be because of the adsorption
of lipids from the industrial and domestic waste or the process of lysis in
which lipids are generated as a result of breakage of cell membranes.
Fig. 2 shows the schematic representation of the overall biodiesel
synthesis process from the sewage sludge.
From the interpretation of the published literature by various re-
searchers around the globe, it is indicated that lipids contained in
sewage sludge are a potential feedstock for biodiesel production, which
along with the economic impact on the waste management solution can
also be a promising alternative [40–43].
Karbgo (2010) [44] first reported in 2010 analysing the research in
the duration of 2007–2010. This review article emphasised the chal-
lenges in the best way of collecting the different fractions from primary
sludge and secondary sludge and their treatment for maximum lipid
extraction. Siddiquee and Rohani reviewed the different lipid extraction
techniques and their conversion to biodiesel [40]. Gaeta-Bernardi and
Parente (2016) [42] recently reviewed the literature and centred their
A.P. Bora, et al.
Fig. 2. Overall biodiesel production scheme from raw sludge [40]
studies on feasibility analysis on the economic aspects of using sewage
sludge as a primary source for the production of biodiesel.
This previous literature concentrated on the limited spectrum of bio-
fuel production from sewage sludge and didn’t portray an inclusive and
updated picture. The current review article is endeavoured to cover all
the aspects of biodiesel and bio-oil production from sewage sludge viz.
sludge collection, pre-treatment, extraction, different production
methodologies, and optimization of the parameters for better pro-
ductivity, kinetic models and process economics. All the aspects of the
production processes of biodiesel using in-situ and acid catalysed
transesterification & via cultivated microorganism and bio-oil produc-
tion by pyrolysis & by the supercritical method are discussed compre-
hensively. In addition, the scope for the exploration of modern process
intensification (PI) tools like ultrasound (US) and microwave (MW)
irradiation for both the lipid extraction and core bio-fuel (biodiesel and
bio-oil) production process are discussed.
2. Pre-treatment of raw sewage sludge
Raw sewage sludge is that which is simply obtained from a waste-
water treatment plant (WWTP). Raw primary sludge contains 4–5%
solids (w/v) whereas secondary (activated) sludge contains 1–2% solids
(w/v). Dufreche et al. (2007) [41] used the gravity settling process to
treat the secondary sludge. After removing the supernatant water, the
sludge obtained was reported to consist of 2% solids. Dewatering pro-
cess was followed by centrifugation which was performed for the time
duration of 20 min at the rpm of 3000 resulted into the sludge con-
taining 7–8% (w/w) solids. Further, they used pressure filtration pro-
cess using 80 µm nylon filter followed by a 20 µm one. After the fil-
tration process, the resulting sludge comprised of 12–14% solids. They
reported the use of hydromatrix for the absorption of residual water
although it is a challenging step to be applied on an industrial scale.
Dewatering of sludge is a highly expensive step in the pre-treatment
process which results in a thick sludge that makes lipid extraction from
the dewatered sludge not feasible. However, lipid extraction from dried
sludge was established to be feasible [40].
Mondala et al. (2009) [17] used the gravity settling process for the
concentration of raw primary and secondary sludge samples at 0 °C for
the time span of 24 h. They employed centrifugation at 3000 rpm for a
time of 20 min in order to dewater the sludge followed by freeze drying.
Olkiewicz et al. (2012) [43] collected different types of sludge from
a municipal wastewater plant in Reus (Tarragona, Spain). Blended
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Fuel 259 (2020) 116262
sludge has been obtained by mixing primary sludge (obtained from
primary settler) and secondary sludge (obtained from secondary settler
followed by floating thickener) in the ratio of 65:35. Stabilized sludge
was obtained by treating the blended sludge in an anaerobic digester
followed by dewatering process.
Pastore et al. (2013) [45] collected primary sludge consisting of a
total suspended solids (TSS) of 4.4 ± 0.15%, which when centrifuged
at 3000 rpm for 10 min resulted in a dewatered sludge with a TSS of
14.4 ± 0.2%. The TSS of the activated sludge obtained from a biolo-
gical treatment plant’s recycling line was not reported by the authors.
However, the TSS of dewatered activated sludge after centrifugation at
3000 rpm was found to be 12.5 ± 0.2%.
Olkiewicz et al. (2015a) [46] used ultrasound and mechanical dis-
integration process for the pre-treatment of the three types of sludge
viz. primary, secondary and blended along with the acid treatment with
concentrated HCl. The pre-treatment method by ultrasound and me-
chanical means was ineffective in the increase in the lipid extraction
considerably. The acidic treatment was observed to be less efficient as
well when compared with the non acidified extraction; however, it
produced a high number of saponifiable lipid.
Patiño et al. (2018) [47] considered three techniques to treat the
raw sludge, a) solid-liquid extraction, b) in-situ transesterification, c)
liquid-liquid extraction. In the process of solid-liquid extraction, de-
watered sludge was dried for 24 h followed by comminuting into fine
particles with the particle size range of 150–250 µm. Crushing has been
done to increase the contact area between the solids and extracting
solvent for efficient lipid extraction. Dried sludge obtained from this
process has been used as a feedstock for the former two cases. While in
the third case of the liquid-liquid extraction process, the collected
sludge after settling process was subjected only to an organic phase for
the purpose. The compositions of primary and secondary sludge ob-
tained from different sources are summarized in Table 1.
3. Extraction of lipids from municipal wastewater sludge:
Boocock et al. (1992) [51] performed two major extraction path-
ways: Soxhlet extraction method and boiling extraction method to
produce low nitrogen and low sulphur substrate. They performed ex-
traction by using two solvents-toluene and chloroform. They observed
that chloroform is not a suitable solvent due to environmental concerns.
They concluded that soxhlet extraction method (dried sludge (50 g),
300 mL Solvent) and boiling extraction method (dried sludge (100 g),
A.P. Bora, et al. Fuel 259 (2020) 116262

Table 1
Composition of sludge obtained from different sources.
Primary Sludge Secondary Sludge Blended Sludge Stabilized Sludge Pulp& Paper secondary waste Reference
water sludge

C 483 ± 12.01 (g/kg TS) 421 ± 15.19 (g/kg TS) 451 ± 9.60 (g/kg TS) 567 ± 14.61 (g/kg TS) [48,49,50]
40.6% (on a dry and ash free
basis)
48.74 ± 0.32 (% dry basis)
H 7.1% (on a dry and ash free [49,50]
basis)
8.96 ± 0.26 (% dry basis)
N 33.82 ± 0.69 (g/kg TS) 49.91 ± 2.38 (g/kg TS) 37.14 ± 1.11 (g/kg TS) 15.14 ± 1.82 (g/kg TS) [48]
1.5–4.0 (%TS) 2.4–5.0 (%TS) [26]
7.7% (on a dry and ash free [49,50]
basis)
6.03 ± 0.14 (% dry basis)5
O 41.2% (on a dry and ash free [49,50]
basis)
29.62 ± 0.25 (% dry basis)
S 3.3% (on a dry and ash free [49,50]
basis)
2.14 ± 0.11 (% dry basis)
VM (Volatile Matter) 60–80% 59–68% 2.5 ± 0.6% 15.6 ± 2.8% [26]
3.3 ± 0.9% 2.8 ± 0.5% [46]
54.2% (on a dry basis) [49,50]
11.31 ± 0.48 (wt%, as per
received basis)
TS (Total solids based on 27.58 ± 1.18 (g/l) 25.36 ± 0.95(g/l) 25.65 ± 0.56(g/l) 25.3 ± 4.4% 26.02 ± 1.48 (g/l) [48]
dry sludge) 5–9% 0.8–1.2% [26]
4.2 ± 1.2% 3.2 ± 0.7% 3.1 ± 0.7% [46]
Energy Content 23000–2900 (kJ/kg TS) 19000–23000 (kJ/kg TS) [26]
11.1 (MJ/kg) [49,50]
14.26 ± 0.34 (MJ/kg)
Water 5.6 (wt%) [49]
83.05 ± 0.54 (wt%, as per [50]
received basis) [25]
0.8 (wt%)
Protein 20–30 (%TS) 32–41 (%TS) [26]
Cellulose 8–15 (%TS) 7–9.7 (%TS) [26]
19.3 (wt%) [25]

Weight as per dry basis.

600 mL Solvent) yielded 12 wt% lipid and 17–l8 wt% lipid respectively.
Dufreche et al. (2007) [41] used three pure solvents hexane, me-
thanol and acetone, a mixture of hexane, methanol, acetone (HMA),
and supercritical (SC)-CO2 as solvents for the extraction of lipid from
the pre-treated sludge. The polarity of the solvents was observed to be
the most significant parameter which resulted in higher oil extraction
for polar solvents. However, the saponifiable lipid content was found in
less number in the case of polar solvents. The sequential extraction with
HMA was observed to be insignificant in the extraction of the saponi-
fiable oil with the successive extraction step. The extraction with the
SC-CO2 showed an increase in the saponifiable oil extraction with the
addition of little quantity of methanol.
Siddiquee and Rohani (2011b) [52] performed a factorial design
process for lipid extraction from primary and secondary sludge using
methanol and hexane as organic solvents. They defined three para-
meters which affect the lipid extraction viz. ratio of solvent to sludge
(ml/g), temperature (°C) and time of extraction (h). For the extraction
with methanol, the temperature was the most significant parameter
followed by solvent to sludge ratio. For extraction with hexane tem-
perature and solvent to sludge ratio both were found to be equally
significant along with the interaction with all the parameters, although
the overall response of the model was lower due to the non-polar nature
of the solvent. Even though methanol and hexane were both suitable to
be used as solvent for the lipid extraction from primary sludge, however
methanol was advantageous in the case of lipid extraction from sec-
ondary sludge.
Zhu et al. (2014) [53] reported three extraction methods viz. hy-
drolysis, Soxhlet and water bath shaking for the extraction of lipid from
the sludge using various organic solvents. Polar solvents were observed
to be more efficient for extracting polar lipids compared with non-polar
solvents. Among the three methods, conventional soxhlet extraction
was reported to be the most efficient and achieved the highest yield of
2.5–10.3% lipid.
Olkiewicz et al. (2014) [54] demonstrated a sequential liquid-liquid
extraction process using a batch mixer-settler reactor considering
hexane as the organic phase at ambient temperature. The sequential
step consisting of three stages exhibited an increase in the efficiency in
the lipid extraction. It was observed that acidic treatment of the sludge
increased the lipid extraction efficiency from the primary sludge com-
pared with the standard MgSO4·H2O method. But the same cannot be
concluded for the secondary sludge and blended sludge as the acidic
treatment was ineffective for those cases.
Melero et al. (2015) [27] used methanol and n-hexane for the ex-
traction of lipid from the primary sludge and achieved an oil yield of
13.6 and 7.4% respectively. The reported results revealed a significant
difference in the oil yield in terms of FFA (Free Fatty Acid) and gly-
ceride fractions, primarily affected by the polarity of the solvent. Al-
though the secondary sludge exhibited a lower amount of oil yield
compared to the primary sludge, it produced saponifiable matter in
very high proportion.
Olkiewicz et al. (2015b) [55] utilised two types of ionic liquids viz.
Tetrakis (hydroxymethyl) phosphonium chloride and 1-butyl-3-methy-
limidazolium methyl sulfate for the extraction purpose from the raw
primary sludge and the results obtained were compared with the con-
ventional soxhlet process. It was observed from the results that the li-
quid-liquid extraction with ionic liquids exhibited nearly equal oil yield

4
A.P. Bora, et al.
from the wet sludge as compared to that of soxhlet extraction with the
dried sludge. Hence it can be interpreted that the former one is an
economical process by eradicating the highly priced sludge drying step.
Zhang et al. (2016) [56] observed ultrasonication effect on lipid
extraction. As reported, the ultrasound aided extraction was equally
efficient when compared with the traditional extraction method but
with much less time (50 min) and less temperature of operation (25 °C).
The reported drawback of the process was that the extracted lipid
contained impurities. Hence an extra hexane purification step should be
followed to omit the impurities.
Li et al. (2018b) [50] performed lipid extraction with different
mixed solvents (methanol–water (MeOH–H2O), n-hexane–water
(HEX–H2O) and they studied the effect of different solvents on oil yield.
They proposed that different product distribution in different mixed
solvents was due to their interaction effect (between organic solvent
and water) during biomass liquefaction.
Olkiewicz et al. (2014) [54] suggested that the lipid-extracted-
sludge (LES) be digested anaerobically in order to obtain biogas con-
sisting of methane and carbon dioxide. Another possibility of treating
LES could be its deployment in the construction industry. The in-
formation on the treatment possibilities of LES is very scant in open
literature and research in this direction is warranted.
In this context, it could be emphasized that extraction of lipid from
the sludge is vital in determining the economy of the process and it
mainly depends upon the choice of solvent [44]. Thus, numerous re-
searchers have suggested different ways to perform extraction
[9,14,17,25,41,52,54,57]. Different conclusions were drawn using
chloroform, hexane, methanol and ethanol as solvents [25,41,52,57].
Although, previous results are not comparable because of various ex-
perimental conditions maintained and parameters utilized. Conse-
quently, general conclusions are hard to be extracted, making it com-
plicated to anticipate the characteristics of other sludges. The previous
findings of various authors related to the extraction of lipid using dif-
ferent organic compounds are listed in Table 2.
4. Biodiesel/bio-oil production from sewage sludge
There are four methods for producing biodiesel from lipid sources
namely direct use and blending, micro-emulsion, pyrolysis (thermal
cracking) and transesterification. Although the direct use and blending
and micro-emulsion methods are simple they have several dis-
advantages like higher viscosity, lower volatility and reactivity of un-
saturated hydrocarbon chains, contamination of lubricating oil, and
lead to the carbon deposition in the engine [58,59]. Vegetable oils,
when undergone pyrolysis process produce biodiesel of high cetane
number, low viscosity, and low sulphur content while it contains an
unacceptable amount of ash and carbon content [60]. Transesterifica-
tion is most widely used over the other methods for the synthesis of
biodiesel as it has the advantages of easier production technology and
results in better yield [61–63]. Table 3 compares the different biodiesel
production methods.
4.1. General background of transesterification for biodiesel production
Transesterification or the alcoholysis is the reaction of triglyceride
(C14-C20) present in lipid sources with primary alcohols (C1-C2) with or
without the presence of the catalyst. In other words, this reaction can be
described as the reaction of the acyloxy (alkoxy promoiety) group of an
ester compound with another alcohol. The basic transesterification re-
action is represented in Scheme 1 showing the overall production of
biodiesel having glycerol as the main by-product [7].
R1, R2, R3 in Scheme 1 are called fatty acid chains consisting of long
hydrocarbon chains [64]. The reaction is consisting of a series of re-
versible reactions where triglyceride reacts with the primary alcohol
and gets converted to diglyceride followed by monoglyceride and gly-
cerol in the consecutive steps [60,65–67]. The overall reaction scheme
5
Fuel 259 (2020) 116262
is represented in Scheme 2 where R4 represents the alkyl group.
The transesterification reaction is thermodynamically reversible in
nature. Stoichiometrically excess quantity of the alcohol should be used
to shift the equilibrium so as to maximize the ester yield. The primary
alcohol used in this reaction is a major feedstock; methanol and ethanol
are being extensively used. Methanol is more preferable due to its
characteristics viz. high reactivity, hydrophobicity, prevention of sa-
ponification, favourable physicochemical properties (polarity and short
carbon chain) and no formation of an azeotrope with water which
makes it easily recoverable in the purification step of biodiesel pro-
duction [7,68,69]. Even though the toxicity level of ethanol is appre-
ciably lower than that of methanol, the former one is hygroscopic,
which is a negative characteristic for considering it as a reactant for the
transesterification reaction as it will enhance the soap forming side
reaction that results in decrease of the biodiesel yield [7]. However, an
extra carbon atom of the ethyl esters attributes to the slightly higher
calorific value and cetane number in addition to the better cold flow
properties [70,71].
The yield of biodiesel via transesterification is influenced by many
factors which include the type of catalyst and catalysis, molar ratio of
oil to alcohol, catalyst loading, operating reaction temperature,
moisture and free fatty acid (FFA) content of the raw oil [40,72,73].
4.1.1. Homogeneous alkali/acid catalysed transesterification
The common alkaline catalysts like potassium hydroxide, potassium
methoxide, sodium hydroxide and sodium methoxide are widely har-
nessed due to their fast reaction rate and high yield of esters
[40,60,66,71,74–77]. The alkali catalysed transesterification must be
essentially anhydrous and the raw oil must be free from the presence of
FFA content to less than or equal to 1% [78]. Otherwise, it would en-
hance the soap forming side reactions, which leads to the increase in
the viscosity of the product and gel formation and thereby hinders the
product separation [79,80]. The higher acidity of the oil (Scheme 3)
minimizes the conversion efficiency of the catalyst and leading to the
soap formation with both surplus and an inadequate amount of catalyst
[77,81].
The presence of moisture in a higher quantity of the reactants fa-
cilitates the formation of water in the saponification reaction or they
hydrolyse the triglyceride into diglyceride and FFA and thereby de-
crease the biodiesel yield, making the transesterification reaction det-
rimental, represented in Scheme 4 [72].
Acid catalysed esterification is used for transforming high FFA
content feedstock into biodiesel. Even though this reaction is approxi-
mately 4000 times slower than the alkali catalysed transesterification
and requires a higher molar ratio of alcohol to oil and higher operating
temperature, it produced higher quantity of esters [40,60,82–84].
Scheme 5 represents the acid catalysed esterification.
Sulphuric acid (H2SO4) and hydrochloric acid (HCl) are extensively
used as acid catalysts [82,83,85], but for industrial biodiesel produc-
tion, the latter one is not preferred due to its corrosiveness [10]. With
the requirements of the higher amount of alcohol and severe reaction
conditions, the biodiesel production with H2SO4 as catalyst also has
limitations viz. the generation of neutralization waste, higher biodiesel
processing cost and risk of sulphur contaminated product [86,87].
Biodiesel can also be produced from the high FFA containing feedstock
with a two-step acid-base catalysis process which involves firstly the
minimization of FFA content by acid esterification and secondly the
transesterification by alkali catalyst, but glycerol separation required in
both the steps had limited its application [84,88,89]. The disposal
problem of contaminated water associated with the homogeneous cat-
alyst (alkali or acidic) in the water washing step, wastage of catalyst,
decrease in ester yield and reusability of catalyst issues can be eradi-
cated to a certain degree by utilizing the heterogeneous and enzymatic
catalysts [10].
A.P. Bora, et al. Fuel 259 (2020) 116262

Table 2
Extraction of lipids from municipal waste water sludge.

(continued on next page)

6
A.P. Bora, et al.
Table 2 (continued)
Lipids yields were calculated based on weight of dry sludge.
Primary and secondary at a ratio of 65:35, v/v.
Polar solvents extracted more polar lipids than nonpolar solvents.
Lipids in primary sludge are mostly nonpolar whereas lipids found in secondary sludgemainly contain polar lipids.
4.1.2. Heterogeneous alkali/acid catalysed transesterification
The frequently used heterogeneous catalysts are CaO, KOH/NaX
impregnated zeolite, potassium doped zirconia, alumina-silica sup-
ported K2CO3 etc (basic) and sulphated zirconia, carbon-based solid
acid catalyst, and carbohydrate derived catalyst etc (acidic). The het-
erogeneous catalysis is advantageous in the context of easy separation,
reusability of catalyst and moderate energy requirement during pro-
cessing, which made it a vital method for commercial biodiesel pro-
duction [15,88,90]. Base heterogeneous catalysts are very efficient in
7
Fuel 259 (2020) 116262
the terms that they are non-corrosive, environmentally compassionate,
recyclable, easy separation from the product and longer catalyst life-
time [63,72]. But this type of catalyst does not display efficient bio-
diesel yield for high FFA and moisture content oil feedstock [63].
However, the acid heterogeneous catalyst can deal with the high FFA
feedstock by avoiding the undesired saponification reaction [91,92].
Many researchers have investigated that extracellular and in-
tracellular lipases are the two classes of enzymes which can act as
catalysts for the transesterification and esterification reactions for
A.P. Bora, et al. Fuel 259 (2020) 116262

Table 3
The different production methods of biodiesel.
Production method Procedure Merits Demerits

Direct use and blending Mixing of vegetable oil, animal fats with organic solvents or
alcohols
Micro-emulsion Mixing of solvent of vegetable oil/ animal fats with alcohol or
blendingof different alcohols
Pyrolysis/thermal Thermo-chemical decomposition of oil at high temperature
cracking facilitated the breaking of high molecular compounds into
short chain hydrocarbons derived fuel oil
Transesterification Mixing of vegetable oil or animal fats with the alcohol in the
presence of catalyst: acid (homogeneous, heterogeneous), base
(homogeneous, heterogeneous) and enzymatic
Modern process intensifying techniques like ultrasound and
microwave are now used to enhance the reaction and
maximize the yield
Simple methodology, lower viscosity
Simple methodology
High purity, approaching the property of
original diesel
The diversity of raw materials irrespective
of acidity or basicity, low production cost
and lower viscosity
Lower carbon decomposition
Low boiling point, higher kinematic
viscosity, coke formation in the long
term use
Complex reaction, lower yield
Poor low temperature performance,
industrial implementation difficulty

biodiesel production [80]. The immobilisation of the lipase catalyst
omits the downstream processing steps such as glycerol separation and
recycling of the catalyst. In addition, immobilisation of the lipase cat-
alyst ensures no side reactions and soap formation hence offering a
greater yield of esters [72,93]. But this process faces technical diffi-
culties like slow reaction rate, deactivation of lipase in existence of
higher quantity of alcohol and higher costs [94].
Saka and Kusdiana (2001) [95] developed a novel supercritical
methanolysis process for transesterification of oil without the presence
of a catalyst. Additionally with this process biodiesel could also be
produced from high fatty acid content oil without any saponified pro-
ducts and high yield of esters was reported with the advantage of simple
separation of the biodiesel from the glycerol along with the tolerability
of the process with the presence of water [96]. However, with the ex-
treme reaction conditions of high temperature (350 °C) and pressure
(43 MPa), it instigated the breakage of unsaturated fatty acid while the
trans-isomerisation adversely affects the fluidic behaviour of the pro-
duct at cold atmospheric condition [97,98]. In Table 4 different cata-
lysts and reaction conditions employed for the production of biodiesel
are summarized.
4.1.3. Transesterification of lipids extracted from sludge
The biodiesel production from the lipid extracted from sewage
sludge was first reported by Dufreche et al. (2007) [41]. The biodiesel
yield of 4.41 wt% (the basis of the total dry weight of activated sludge)
was obtained from the ex-situ transesterification process while the in-
situ acid catalysed transesterification in which lipids are directly con-
verted to biodiesel without the presence of the extraction step yielded
6.23 wt%.
Mondala et al. (2009) [17] investigated the in-situ transesterifica-
tion process with the presence of H2SO4 catalyst (5% v/v) and obtained
a biodiesel yield of around 14 wt% and 2 wt% respectively for primary
and secondary sludge at a reaction condition of 75 °C and methanol to
sludge (M/S) mass ratio of 12:1.
Yu et al. (2010) [117] used microwave irradiation to study the ef-
fect of contact time and microwave energy on sludge disintegration.
Microwave irradiation released the organic matter in the flocs together
with the disintegration of the sludge and contributed to the death of
microbial cells. All these conclusions can be attributed by the increase
in SCOD (soluble COD), turbidity, VSS (volatile suspended solids) so-
lubilization, EPS (extracellular polymeric substances) content and in-
organic nitrogen and with the decrease in settling velocity. According to
them the temperature of sludge was found to be the most significant
parameter affecting the physicochemical properties of the sludge. Due
to the high-frequency electromagnetic radiation contacted with the
dipolar molecules, rapid molecular rotation started which evaporated
the water in the sludge by the increase of contact time. Additionally, the
correlation analysis established the microwave contact time to be the
primary factor for improving the sludge settleability and solubility of
organic matter.
Siddiquee and Rohani (2011b) [52] investigated the biodiesel pro-
duction of H2SO4 catalysed esterification and transesterification from
the lipid extracted from the dried primary and secondary sludge. On the
basis of mass fraction of the lipid around 40% esters yield was obtained
from the primary sludge for both hexane and methanol. On the other
hand the secondary sludge yielded maximum 30% FAME with me-
thanol as the organic solvent. The yield increased by approximately 18
(wt/wt) % by using natural zeolite in addition to the catalyst which acts

Scheme 1. Transesterification reaction.

8
A.P. Bora, et al.
Scheme 2. Transesterification reaction scheme [60,65–67]
as a dehydrating agent.
Huynh et al. (2012) [118] used water both as the hydrating agent to
increase the efficiency of extraction and catalyst for the conversion of
lipids into FAME under subcritical conditions of 175 °C, 3.5 M Pa and
M/S ratio of 30 mL g−1. Around 90% conversion of lipids was obtained
in the time span of 24 h with the usage of water as the catalyst also
facilitated the easy separation of the product with the minimisation of
processing cost.
Olkiewicz et al. (2012) [43] used a modified version of Christie’s
method [41,119] to produce biodiesel and reported the highest yield
(based on the dry weight of sludge) of 13.9% from the primary followed
by 10.9% from the blended sludge. The secondary and stabilized sludge
performed inferiorly with producing 2.9% and 1% biodiesel respec-
tively. The large quantity of organic matter present in the primary
sludge signifies the higher biodiesel yield from it.
Pastore et al. (2013) [45] used dewatered sludge (Total suspended
solid: 15 wt%) as the raw material to eliminate the step of sludge
drying. The energy input of 17 MJ per kg FAME produced a yield of
18% esters by a two-step process; firstly extraction of lipids from the
dewatered acidified sludge using sulphuric acid and secondly the me-
thanolysis. The usage of sulphuric acid is significant as it converted the
triglycerides into biodiesel along with the conversion of soaps into fatty
acids by esterification with methanol. The valorization of primary
sludge was also conducted to produce valuable chemicals viz. sterols,
9
Fuel 259 (2020) 116262
aliphatic alcohols and waxes.
Zhang et al. (2013) [120] used the methanol to lipid molar ratio of
6:1, H2SO4 catalyst (1 v/v %) and temperature of 50 °C as the operating
parameters in a two-step biodiesel production process. The authors also
investigated the one-step process for biodiesel production where dried
sludge was directly used for transesterification at 50 °C for 4 h in the
presence of H2SO4 catalyst. The two-step process with a total energy
input of 12.4 GJ for the generation of 1-ton of biodiesel is more efficient
and feasible than the one-step process with an energy input of 17.3 GJ.
Choi et al. (2014) [121] presented an alternate method for produ-
cing biodiesel from wet wastewater sludge by using xylene as the sol-
vent for in-situ transesterification instead of hexane with H2SO4 as the
acid catalyst. The biodiesel yield was reported to be 8.12%, which is 2.5
times higher than that obtained using hexane as a solvent.
Melero et al. (2015) [27] employed Zr-SBA-15 as catalyst under the
reaction conditions of 209 °C, 2000 rpm, and 12.5 wt% (basis of lipid
mass) catalyst loading. The saponifiable fatty acids and glycerides were
transformed superiorly by the one-step process in comparison to the
two-step one keeping the same reaction condition of 65 °C and 3 h of
time. The highest observed yield of esters was around 15% using the
sludge from the primary source via the one-step method. They also
tested the intolerance of the used catalyst against water and by getting
the same yield of esters as with the dry sludge it was concluded that the
comparatively lower acidic strength of the catalyst inhibited the
Scheme 3. Saponification reaction of free
fatty acid (FFA).
A.P. Bora, et al.
Scheme 4. Hydrolysis of triglyceride in the presence of moisture content.
hydrolysis of the produced esters and accordingly resulted into higher
yield.
Tran-Nguyen et al. (2015) [122] carried out research using a sub-
critical mixture of methanol and acetic acid for the transesterification of
sludge. A high temperature of 250 °C and solvent (85% methanol and
15% acetic acid) to sludge ratio of 5 (mL g−1) were maintained and
reported a FAME yield of 30.11% at time duration of 30 min. On the
other hand, when acid catalysed (4% v/v H2SO4) transesterification
was employed, a higher yield of 35% was obtained but this process
required a very long-time duration of 24 h at 55 °C and an M/S ratio of
25 (mL g−1).
Urrutia et al. (2016) [123] employed acid (H2SO4) and enzymatic
(Novozym 435) catalyst for the synthesis of biodiesel using greasy &
secondary sludge as a feedstock. The catalyst duo executed parallel
conversion of free fatty acids (FFA) and triacylglycerols (TAG) to the
FAME. The acid catalysis backed esterification of FFA was superior to
that of the transesterification of TAG. It was observed that the enzy-
matic catalyst initially hydrolysed the TAG to the FFA followed by es-
terification to the methyl esters. The highest FAME yield of around 63%
was obtained for greasy sludge utilising the acid catalyst while it was
around 58% for the enzymatic catalyst.
Olkiewicz et al. (2016a) [124] used various kind of ionic liquids and
imidazole both assisted with the sulfonic group and different anions for
the conversion of sludge derived lipid into biodiesel. They reported that
4-(3-methylimidazolium) butane sulfonic acid tri-
fluoromethanesulfonate, and [mimC4SO3H][SO3CF3], were superior to
the other equivalent ammonium ionic liquids (4 (trihexylammonium)
butane sulfonic acid trifluoromethanesulfonate, and [N666(C4SO3H)]
[SO3CF3]) tested in terms of better reactivity of the catalyst and higher
product quality. The FAME yield of 90% (based on saponifiable lipids)
was obtained by using [mimC4SO3H][SO3CF3] as a catalyst under the
optimum reaction conditions of 10:1 M ratio of methanol to saponifi-
able lipids, 7 wt% catalyst loading (based on wt% of lipids), 100 °C and
time of 5 h. They also concluded that with the advantages of easy
product separation from the product mixture, reusability of catalyst and
resistance to saponified product irrespective of the quality of the
feedstock, these ionic liquid catalysts are efficient and environment-
friendly than the conventional sulphuric acid catalyst.
Zhang et al. (2016) [56] studied the in-situ transesterification pro-
cess with the assistance of ultrasound (20 kHz, 750 W). The reaction
10
Fuel 259 (2020) 116262
under ultrasonication achieved equilibrium within a much shorter time
(30–40 min) compared to that of without ultrasonication (6–12 h). With
the increasing H2SO4 concentration from 1 to 2% (v/v methanol), the
yield of esters increased from 89 to 93% with ultrasonication and 83 to
89% without ultrasonication. However, the increment in catalyst
loading from 2 to 5% (v/v methanol) resulted in the improvement in
the FAME yield in the in-situ transesterification without the assistance
of ultrasound (89–92%) than that with the ultrasound (93–94%) al-
though the latter one obtained the higher yield. The ultrasound assisted
process produced 93% yield with 2% H2SO4 concentration (v/v me-
thanol), whereas without the presence of ultrasound the process needed
5% H2SO4 to deliver the same yield.
Demirbas et al. (2017) [125] did the similar study previously done
by Dufreche et al. (2007) [41]; and Urrutia et al. (2016) [123] to
produce biodiesel from sewage sludge and reported the average yield of
methyl esters from its extracted lipids to be 24%. The total average of
saturated fatty acids obtained was as high as 55.0% of which palmitic
acid (37.5%) was the major saturated fatty acid, followed by stearic
acid (12.0%). The major unsaturated fatty acid obtained was oleic acid
(29.0%) followed by linoleic acid (6.2%).
Choi et al. (2017) [126] proposed a concept of a bio-refinery for
producing both the FAME and biogas from waste activated sludge
(WAS) by performing in-situ lipid extraction followed by anaerobic
digestion. The reported yield of non-polar transesterified product was
9.68% (based on dried mass of WAS) and of FAME was 78.45% (40.7%
saturated content and 59.3% unsaturated content) by maintaining the
optimum reaction conditions of: 10 mL/g of methanol dose, methanol/
hexane volume ratio of 2.5, reaction temperature of 55 °C and reaction
time of 8 h.
Patiño et al. (2018) [47] used acid catalysed in-situ transester-
ification for the conversion of sludge derived lipid into biodiesel. It was
observed that the introduction of the sonication step for the pre-treat-
ment of the sludge considerably increased (more than 65%) the FAME
yield for both the acid and in-situ transesterification with 16 h of re-
action time, whereas 24 h of reaction time needed in absence of ultra-
sonic pre-treatment. The maximum yield was obtained subsequent to
50 min of sonication time as the maximum cell disintegration was at-
tained at that condition and thereby the highest quantity of accessible
lipid was exhibited to the solvent and the catalyst.
Scheme 5. Acid catalysed esterification.
A.P. Bora, et al. Fuel 259 (2020) 116262

Table 4
Summary of different catalysts and reaction conditions employed for the production of biodiesel.
Types of catalysts Feedstock Type of catalyst used Alcohol to oil ratio Reaction Reaction Time Reference
temperature

Acid homogeneous Waste palm oil Concentrated sulphuric acid (1.5–2.25 M) 3h [99]
Jatropha curcas seed oil Sulphuric acid (1% w/w) 0.60 (w/w) 50 °C 1h [89]
Acid heterogeneous Palm kernel oil sulphated zirconia (SO42-/ZrO2) [100]
Crude coconut oil [101]
Soybean oil unsulphated zirconia (ZrO2) 2.33:5(on weight 70 °C 9h [102]
Vegetable oil chloroaluminate ([Et3NH]Cl-AlCl3) basis) 75 °C 140 h [103]
Yellow horn (Xantho sulphated zirconia (SO42 /ZrO2) and 70 °C 10 min
cerassorbifolia Bunge) oil tungstated zirconia (WO3/ZrO2) 12:1 (on molar basis)
Cs2.5H0.5PW12O40 Heteropoly acid
Base homogeneous Waste cooking oil Potassium hydroxide (KOH) 6:1(on molar basis) 70 °C 1h
[104]
Base heterogeneous Sunflower oil CaO 6:1 (on molar basis) 60–120 °C 1.5–5.5 h [105]
Palm oil BaO 3:1–15:1 (on molar 10–60 min [106]
Palm oil KOH/AC basis 70 °C 15 h [107]
Soybean oil Kalsilite (KAlSiO4) 15:1 (on molar basis) 120 °C [108]
Waste eggshells CaO 1:9 (on molar basis) 65 °C [109]
Waste cooking oil KOH loaded on alumina 9:1 (on molar basis) 70 °C 2h [104]
Sunflower oil Calcined calcium zincate 7:1 (on molar basis) 400 °C 3h [110]
Soybean oil and waste frying CaO 12:1, 9:1, 6:1 (on 60 °C 2h [111]
oil K2MgSiO4 molar basis) 60 °C [112]
Soybean oil Potassium 6:1 (on molar basis) 60 °C 8h 113[114]
Palm oil Sodiumsilicate 25:1 (on molar basis)
Soybean oil
Supercritical Conditions Vegetable oil 6:1–40:1 (on molar 250–400 °C [115]
Rapeseed oil basis) 350and 400 °C [95]
1:42(on molar basis)
Enzymatic catalyst Palm oil IM B. cepacialipase 30 °C 72 h [116]

4.2. Biodiesel production from sludge cultivated microorganism
Along with the conversion into methane (CH4) and carbon dioxide
(CO2) from the sewage sludge, the lipid can be obtained from the
carbon moieties contained in the sludge by aerobic microorganisms. It
is reported that yeasts can accumulate maximum 70% of lipids in dry
matter [127]. First data in lipid storage and the conditions to be
maintained for the fermentation were reported by Mulder et al. (1962)
[128]. A high carbon to nitrogen (C/N)-ratio is required for the growing
of lipid accumulation by the organisms. Out of the yeast considered for
studies Lipomyces starkeyi was reported to store large amounts of lipids
when grown on sludge media [129]. The microbes that can accumulate
more than 20% (g/g) lipid are named as oleaginous microbes [130].
From the known 60,000 fungal species, hardly 50 species can accu-
mulate lipid content more than 25% [130,131]. The employment of
oleaginous microorganisms can lower the production cost of oil as they
accumulate lipids within a short span of time and can easily grow in
various agricultural and industrial waste environments [132]. Ad-
ditionally, unlike the vegetable oils the oleaginous microorganisms’
culture is not affected by any seasonal or climatic conditions.
The potential of accumulation of lipids by Lipomyces starkeyi when
grown on sewage sludge was observed by Angerbauer et al. (2008)
[132]. The maximum lipid content obtained at the C/N-ratio of 150 was
68% (w/w) while 40% (w/w) lipids were accumulated at the C/N-ratio
of 60. The pH value of 5.0 was found to be dominant for the max-
imization of accumulation of lipids. Even though the synthetic medium
had not hindered the growth of Lipomyces starkeyi microorganisms but
there was no noteworthy growth of the microorganisms in the raw
untreated sludge. However, lipid accumulation can be increased by
employing the pre-treatment methods. The maximum value of 1 g L−1
was attained by incorporating the sonicated sludge samples.
Zhang et al. (2014) [48] observed that secondary and pulp & paper
sludge provide a compatible environment for the microorganisms to
grow for the lipid accumulation when compared to the primary and
mixed sludge owing to the higher carbon availability. It was reported
that the addition of glucose in the sludge sample (C/N ratio 100) re-
sulted in a higher accumulation of P. amethionina sp. SLY whereas the
addition of glycerol resulted in the higher lipid accumulation of Ga-
lactomyces sp. SOF and Trichosporon oleaginosus.
Sun et al. (2015) [133] studied the effect of pH on upgrading bio-
diesel synthesis by culturing special microbial communities from mu-
nicipal activated sludge. The results showed that pH of about 7.5 as-
sisted the faster production of biomass and accumulation of lipid at the
initial glucose loading of 40 g COD L−1 and COD:N ratio of 90:1.
Comparing the biodiesel yield of 5.2 mg/(g dry sludge) obtained with
seed sludge, the cultivated sludge could produce higher yields of
69.3 mg/(g dry sludge) and 63.3 mg/(g dry sludge) with and without
controlling pH respectively. But the higher amount of unsaturated fatty
acid esters (64%, w/w total FAME) which could be helpful in improving
flow characteristics of biodiesel in the ignition engine were synthesised
from cultured sludge without pH control. However, pH control could
promote the cultivation of bacteria like Shewanella etc. in the cultured
sludge which positively contributed to increase the biodiesel yield.
The dynamics of the FAME profile and diversity of microbial or-
ganisms in the activated sludge in the course of lipid accumulation on
short chain fatty acid (SCFA) as a carbon source was investigated by
Fortela et al. (2016) [134]. Acetic acid buffered with sodium acetate
was employed as the model carbon source coupled with ammonium
sulphate as the nitrogen source. The grab-activated sludge was fed to
the bioreactor and the FAME profile obtained in each run was analysed.
The cultivation on acetic acid stabilized the FAME profile of activated
sludge which was attributed to the increase of budding yeasts.
Selvakumar and Sivashanmugam (2017) [135] investigated the ef-
fect of thermo-chemo-sonic on pre-digestion of municipal Waste Acti-
vated Sludge (WAS) to cultivate oleaginous L. starkeyi MTCC-1400 as a
model organism for the production of biomass and lipid with high yield.
The reduction of higher suspended solids (SS) and solubilisation of
chemical oxygen demand (COD) were obtained at specific energy (SE)
input of 5569 kJ/kg when WAS was processed with sodium hydroxide
and potassium hydroxide respectively. The highest 17.52 g L−1 biomass
and 64.3 wt% lipid were obtained in the pre-digested sample of NaOH.
The lipid profile contains primarily palmitic acid and oleic acid at
45.6% and 38.7% respectively. However, the authors did not evince the
details of individual effect of ultrasonic parameters on the pre-digestion

11
 Table 5
Comparison of results of producing biodiesel from sludge by various methods.
Sources of activated sludge Lipid content (%) (on Production method Methanol to Temperature (°C) Time (h) Pressure FAME yield (wt%) (on the basis Conversion (%) Reference
A.P. Bora, et al.

the basis of dry sludge/lipid (MPa) of dry sludge)

sludge) massratio
(mL g−1)

Municipal wastewater treatment plant 27.43 Acid catalyzed (H2SO4 1% v/v) 5 50 24 6.23 22.71 [41]
in-situ transesterification
Municipal wastewater treatment plant n.r. Acid-catalyzed in-situ 12 75 8 14.50 (primary sludge) 97.89 [17]
Primary sludge transesterification (H2SO4 5% v/ 2.50 (secondary sludge)
Secondary sludge v)
Municipal wastewater treatment plant n.r. Acid-catalyzed in-situ 30 55 24 4.79 [14]
transesterification (H2SO4 4% v/
v)
Municipal wastewater treatment plant Extraction with Acid-catalyzed 50 60 24 Extraction with methanol: [52]
methanol: 14.46 transesterification (H2SO4 2% v/ 26.84 (primary sludge)
(primary sludge) v) 30.28 (secondary sludge)
10.04 (secondary Extraction with hexane: 41.25
sludge) (primary sludge)
Extraction with 38.94 (secondary sludge) (on
hexane: 11.16 the basis of lipid)
(primary sludge)
3.04 (secondary
sludge)
Municipal wastewater treatment plant n.r. Acid-catalyzed in-situ 30 75 24 3.93 [18]
transesterification (H2SO4 10%
v/v)
Uni-President Enterprises Corp. Ltd., Chung- 66.64 Subcritical water-subcritical 30 175 8 3.5 45.58 66.52 [118]

12
Li Bakery Factory methanol
Municipal wastewater treatment plant 25.3 (primary Acid-catalyzed 20 50 24 13.9 3 (primary sludge) 55.053 (primary [43]
sludge) transesterification (H2SO4 1% v/ 10.9 (blended sludge) sludge)
21.9(blended sludge) v) 2.9 (stabilized sludge) 49.77 (blended
10.1 (stabilized 1 (secondary sludge) sludge)
sludge) 28.71 (stabilized
9.1 (secondary sludge)
sludge) 10.98 (secondary
sludge)
Wastewater treatment plant n.r. Acid-catalyzed (H2SO4 0.05% v/ 10 55 8 9.68 [121]
v, n-hexane as co-solvent)
Municipal wastewater treatment plant 44.40 Acid-catalyzed (H2SO4 7 wt%, n- 20 55 7 61.00 5 [136]
(greasy, primary and secondary sludge) hexane as co-solvent 10% v/v)
Waste water treatment plant Universidad Extracted with n- Zr-SBA-15 catalyst, 12.5 wt%, 10 65 3 15.5 (primary sludge) 92% (one step [27]
Rey Juan Carlos, Madrid hexane: 7.4 (primary one step in-situ (secondary sludge) process)
sludge) transesterification and two step 90% (two step
Extracted with extraction followed by process)
methanol: 13.6 transesterification (Conversion with
(primary sludge) respect to
2.1 (secondary extractable
sludge) saponifiable
fraction)
Hsin-Tung-Yang LTD Da-Yuan Factory 45.42 Subcritical methanol-Acetic Acid 5 250 1.5 2.5 30.11 65.97 [122]
(AA 15%)
Municipal wastewater treatment plant 65.4 (Greasy sludge) In-situ transesterification (H2SO4 15 (Acid catalyst) 60 8 (Acid 63.9 (Acid catalyst) [123]
(greasy and secondary sludge) 43.6 (Secondary and Novozym 435 4 (Enzyme catalyst) 58.7 (Enzyme catalyst)
sludge) catalyst) 16 (Enzyme
catalyst)
(continued on next page)
Fuel 259 (2020) 116262
 Table 5 (continued)

Sources of activated sludge Lipid content (%) (on Production method Methanol to Temperature (°C) Time (h) Pressure FAME yield (wt%) (on the basis Conversion (%) Reference
the basis of dry sludge/lipid (MPa) of dry sludge)
A.P. Bora, et al.

sludge) massratio
(mL g−1)

Municipal primary sludge Esterification, 7 wt% ionic liquid 10:1 M ratio of 100 °C 5h 90% (based on saponifiable [124]
catalyst (wt%, based on lipids) methanol to lipids)
saponifiable
lipids
Gangneung wastewater treatment facility, 14.5% using the with Two-step Biodiesel Production 20 mL-methanol/ 70 °C 8h 39.0% (biodiesel yield) [137]
Blended Sewage Sludge ultrasonication Process, 0.2% (g/g-lipid) H2SO4 g-lipid (g-biodiesel/g-lipid)
pretreatment an overall yield (i.e., extraction
and transesterification) 5.3%
(g-biodiesel/g-BSS)
Gangneung wastewater treatment facility, One-step direct process (in-situ), 10 mL of 60 °C 4h 3.1% (g biodiesel/g-BSS) [138]
blended sewage sludge (BSS) 0.7% (g/g-BSS) of H2SO4 methanol/g-BSS
Trichosporonoleaginosus cultivated with 95.3% (w/w) lipid Single step lipid extraction and Mixture of 60 min 95% (w/w) [56]
secondary sludge, local municipal recovery transesterification with chloroform and
wastewater treatment plant ultrasonication, methanol (1:1 v/
(CommunauteUrbain de Qu ebec, CUQ), v)
Quebec, Canada
Municipal wastewater treatment plant in In-situ transesterification by Alcohol and 60ć 8h 6.8% [139]
Beijing, China alkali catalyst (KOH/activated sludge 10:1,
carbon), catalytic amount (3 wt
%)
Anaerobic–anoxic–oxic (A2/O) sludge In situ transesterification Methanol- 60 °C 16.6% with a fatty acid methyl [140]
membrane bioreactor (MBR) sludge (concentration of H2SO4 5% (v/ tosludge mass 50 °C ester purity of 96.7% (4.2%
v)) ratio of 10:1 with a fatty acid methyl ester

13
In situ transesterification Methanol-to- purity of 92.7%
(concentration of H2SO4 5% (v/ sludge mass ratio
v)) of 8:1
Vasant Kunj Sewage Treatment Plant (VK In situ transesterification, 5% 20.76 ± 0.04% [141]
STP), New Delhi, municipal secondary catalyst and 0.16 g/mL sludge
sludge solids,
sewage sludge, wastewater treatment plant Pyrolysis, sludge-derived bio-oil Ethanol to bio-oil 258.5 °C 3.23 h 67.2% biodiesel yield [142]
in College Station, TX, USA using nickel-modified HZSM-5 mass ratio – 2.50
catalyst
Secondary sludge from municipal In situ (Sonication) and 5% of 50 min 17% FAMEs [47]
wastewater, in Villapérez-Oviedo H2SO4
(Asturias, NW Spain)
Fuel 259 (2020) 116262
A.P. Bora, et al.
step.
From the previous literature reported by the researchers, the main
consensus that could be drawn is that the acid transesterification is
more efficient relative to the other available processes, lipid extraction
being the main limiting step. As a consequence, to augment this step a
few of the researchers proposed sonication technology to be a potential
pre-treatment. Sonication technology exhibited high magnitude ultra-
sonic irradiation in the sludge and as a result of the propagation of these
waves, formation and the intense collapse of bubbles occurs which
promoted the cell lysis and ultimately releasing the lipids into the
medium.
Table 5 presents the different methods of biodiesel production
adopted.
Generally, sonication exhibits rapid growth and collapse of cavita-
tion bubbles which intensifies the physical and chemical effects of a
heterogeneous reaction mechanism. The physical effect relates to the
emulsification of the reactant which is formed by the generation of
micro turbulence as a result of radial movement by the bubbles. While,
the chemical affect relates to the release of free radicals during the
collapse of bubbles. The reaction rate is accelerated by the increased
interfacial area in a similar way as a mechanical agitator and by the free
radicals within the bulk reaction mixtures [143]. These advancements
allow the use of ultrasound irradiation as a novel, more competent
integration methodology in biodiesel synthesis from various feed-stocks
[144]. This technology has been used successfully in the recent past for
producing biodiesel utilizing algae as a feedstock or biogas from sludge
[145,146].
4.3. Bio-oil production from sewage sludge
Bio oil or pyrolysis oil is obtained by heating the dried biomass at
the atmospheric condition in a moderate to high-temperature reactor
without the aid of any solvent. It can also be derived by the hydro-
thermal liquefaction of the organic components of the biomass at a low
temperature and high-pressure conditions in the presence of solvents
[147]. The bio-oil is basically consisting of various organic compounds
viz. acids, alcohols, ketones, oligomers etc [148]. The bio-oil is a re-
newable fuel having some fuel properties similar to petrodiesel. How-
ever, it has some major disadvantages that lie in its path of commer-
cialization viz. high acidity, instability, viscosity, corrosiveness and low
heating value etc [149,150]. Being a cheap feedstock it is advantageous
to produce bio-oil from MSS. But sludge derived bio-oil contained a
high quantity of nitrogen and oxygen [151] which inhibited its adverse
fuel properties as mentioned above [152]. Although these properties
limited its application as an alternative fuel for transportation without
modification [142] it could be used for the production of raw materials
like olefins, aromatics and hydrogen or extraction of chemical compo-
nents or direct usage in furnace & boilers [49]. However, the bio-oil
could be upgraded characteristically by blending or emulsifying with
biodiesel to improve the combustion quality of the blended fuel [153].
4.3.1. Bio-oil production from sludge through pyrolysis
Pyrolysis can be defined as the thermo-chemical decomposition
process occurring in the presence of high temperatures and inert at-
mospheres that involves the breaking of high molecular chemical
compounds into simpler molecules producing solid, gaseous and oil
fractions. Capodaglio et al. (2016) [154] induced microwave heating
(2.45 GHz, 3 kW) pyrolysis to obtain biodiesel-like oil, or sewage sludge
pyrolysis oils (SSPOs) from the municipal waste pre-digested sludge.
Although having an inferior lower calorific value (LCV) of the sludge
derived oil than the common vegetable oil-derived biodiesel, other fuel
characteristics are very similar. The LCV of recovered oil of 32.976 kJ/g
found by them is within the specified range of 32–34 kJ/g contrary to
that of corn- and safflower-derived oils at 42–43 kJ/g. Thus, LCV of
sludge derived oil has a 30% lower value than the conventional pet-
rodiesel.
14
Fuel 259 (2020) 116262
A conical spouted bed reactor was designed by Alvarez et al. (2016)
[49] in the temperature range of 450–600 °C for the fast pyrolysis of
sewage sludge. The authors characterised the bio-oil obtained at 500 °C
(achieved maximum yield at this temperature; 77 wt% on a dry ash
free) and observed phenols, ketones, alcohols, amides and nitriles to be
the major organic compounds present. Because of the presence of the
lower amount of oxygenated compounds compared with other lig-
nocellulosic materials, the bio-oil has a higher concentration of C and H
along with the lower heating value (LHV).
Capodaglio and Callegari (2018) [155] stated that the microwave-
assisted pyrolysis (MAP) to be more favourable for the producing bio-
diesel from sewage sludge in terms of energy and economic efficiency.
Pyrolysis can produce different products like solid carbonaceous re-
sidue (char/biochar), liquid (biodiesel), and gas (syn gas) at different
phases which have an enormous potential of replacing currently
available fossil fuel; biodiesel being the most desirable because of its
flexibility and adaptability in current engine hardware.
Arazo et al. (2017) [142] used a nickel-based HZSM-5 catalyst to
produce bio-oil from sewage sludge. The effects of various reaction
parameters on the bio-oil yield along with the degrees of deni-
trogenation and deoxygenation were studied. With the increase of re-
action temperature, the biodiesel yield was observed to be decreased
although the improvement in the removal of both nitrogen and oxygen
were noticed. The optimum set of reaction conditions predicted by re-
sponse surface methodology for the yield of 67.2% bio-oil was a tem-
perature of 258.5 °C, ethanol to bio-oil mass ratio of 2.50 with the re-
action time of 3.23 h.
4.3.2. Bio-oil production from sludge via supercritical fluid conditions
Leng et al. (2018b) [153] used supercritical liquefaction at 300 °C
with methanol as a solvent for the synthesis of bio-oil using sludge
collected from different sources, viz. municipal sewage, paper/pulp mill
and slaughterhouse. This process yields 20–30% of carbon-rich and
viscous bio-oils, containing methyl esters in a significant amount. The
obtained bio-oils were modified by blending or micro emulsifying with
FAME. It was reported that the blending and micro emulsification
processes result in the increase of the decomposition rate and reduction
of activation energy of the hybrid fuel systems. Moreover, improved
ignition qualities of the blended micro-emulsions in the combustion
engine makes it superior compared to the individual usage of either
biodiesel or bio-oil with the key disadvantages like longer ignition
delay and higher viscosity.
The effect of different mixed solvents, viz. methanol–water
(MeOH–H2O), n-hexane–water (HEX–H2O), on the liquefaction of mu-
nicipal wet sewage sludge (WSS) was investigated by Li et al. (2018b)
[50]. They achieved the highest bio-oil yield of 46.5 wt% using
MeOH–H2O containing 37.4% methyl esters and the lowest yield of
10.3 wt% using HEX–H2O. The highest calorific value
(36.45 ± 0.38 MJ/kg) and the lowest oxygen content of bio-oil
(7.65 ± 0.26 wt%) were obtained when using HEX–H2O. The usage of
MeOH–H2O promoted the formation of esters while HEX–H2O not only
facilitated the thermal stability of the solid residue but also increased
the extraction efficiency of aliphatic compounds.
The low bio-oil yield and low fuel characteristics are the main
drawbacks of utilising this fuel in full potential. The requirement of
high temperature in the bio-oil production is not suggested for in-
dustrial scale owing to its high operational cost. Hence catalyst can be
used to produce it at the lower temperature and enhance its fuel
properties without the modern up-gradation technique like emulsifi-
cation. It is recommended to study the fundamental mechanism inside
the pore of the catalyst to understand the catalytic behaviour for the
conversion of bio-oil and thereby predict its yield. In addition, kinetic
studies can be done to further predict the thermal behaviour of sludge
lipid in catalytic pyrolysis.
A.P. Bora, et al.
4.4. Bio-fuel production from the scum sludge
Scum is a floatable by-product of the waste water treatment plant
obtained from the primary and secondary settler tanks. It is primarily
an oil-rich product composed of animal fats, vegetable oils and grease
(FOG), food waste, soaps, plastic waste and different metallic and non
metallic waste from industries [156]. Owing to their lower density,
these oily materials float on the upper surfaces of the clarifiers and form
conglomeration with the other waste materials which can be recovered
for energy utilization. Bi et al. (2015) [157] reported that the scum
sludge contained nearly 60% oil content which has the potential of
becoming an alternative feedstock for bio-oil production along with the
primary and secondary sludge.
Usually, the scum sludge is processed in the anaerobic digester
where the product biogas is utilised for the generation of electricity to
be used in the power plant [158]. But the floated scum on the top layer
of the digester hinders the operation and lowers its efficiency [156]. As
a result, it has been preferred by WWTPs to dispose the scum sludge
directly in the landfills. However, this increases the expenses of the
treatment plant along with the detrimental effect to the environment.
To overcome this problem, a new methodology was developed for
the successful conversion of scum to bio-oil. Bi et al. (2015) [157] de-
veloped a novel process for conversion of scum to biodiesel consisting
of six steps. The acid washing was used for the breakage of the oil-water
emulsion and the conversion of soap present in the scum to FFAs along
with the removal of other impurities. This step was followed by the acid
esterification using sulphuric acid as the catalyst to convert the FFAs
into methyl esters. The produced methyl esters were then converted to
FAME by base catalysed transesterification with potassium methoxide
as the catalyst. Finally glycerol washing was applied to augment the
separation between product biodiesel and glycerine.
Sangaletti-Gerhard et al. (2015) [159] interpreted the biodiesel
synthesis process using wet greasy (WG) sludge and dried greasy (DG)
sludge by in-situ transesterification process. The maximum 61% pro-
duct yield was obtained from WG sludge in the presence of co-solvent
(n-hexane) using an acid catalyst (H2SO4), where at the same reaction
condition DG sludge catalyzed by enzymatic catalyst (Novozym435 li-
pase) reached a yield of around 57%. With the absence of co-solvent
and the presence of sulphuric acid reported yield was 55% for WG and
36% for DG sludge. The higher miscibility of different acylglycerols in
n-hexane assisted the better alcoholysis which was ascribed to the
higher product yield.
Almeida et al. (2016) [160] employed a stirred tank slurry reactor
for the catalytic cracking of scum for the generation of light and heavy
diesel like fractions. The reactor was operated at the temperature and
pressure of 450 °C and 1 atmosphere respectively for the cracking
process utilising activated red mud as the catalyst. The reported yield of
the light diesel-like fraction was around 6 wt% whereas approximately
41 wt% heavy diesel-like fraction was obtained using 5 wt% of the
catalyst for both the cases. The GC–MS analysis showed that the light
diesel-like fraction consisted of nearly 73% of hydrocarbons followed
by the rest oxygenates compounds.
Anderson et al. (2016) [161] used the series of processes including
heated filtration, acid hydrolysis and solvent extraction for the extrac-
tion of oil from the scum. This was followed by the glycerine ester-
ification in order to lower the FFA value below 0.5% (w/w) so as to
carry out transesterification of the product using a base catalyst. The
purpose of the glycerine esterification (the reaction of FFA with the free
glycerine) was to produce monoglycerides and water and thereby era-
dicating the requirement of acid esterification.
Bitonto et al. (2016) [162] reported heating of the sewage scum at a
temperature of 353 K followed by separation by centrifugation to obtain
the near above 90% lipid extract. Further, the lipids were converted to
FAME in a series of three consecutive reactors where the methanol and
aluminium chloride hexahydrate solution were charged counter-cur-
rently. As a final result, about 93% FFAs were converted to FAME using
15
Fuel 259 (2020) 116262
minimal amount of reactant at mild reaction conditions.
It was reported by Mu et al. (2016) [156] that the conversion of
scum sludge to biodiesel was way more profitable than that of the
processing of scum sludge to biogas in the combustor or in the anae-
robic digester. The generation of the revenue was more than 29% and
104% when compared to the combustor and the anaerobic digester
cases respectively.
Yi et al. (2016) [163] used freeze dried scum sludge for the pro-
duction of biodiesel using both ex-situ and in-situ transesterification. It
was reported that the scum sludge had the higher calorific value and
contained higher amounts of neutral lipids in comparison to that of the
primary and secondary sludge. Further, in-situ transesterification for
biodiesel production exhibited approximately 60% (w/w) unsaturated
fatty acids.
Hums et al. (2018) [164] reported approximating the biodiesel
synthesised using the lipid extracted from the brown grease to be of
81% conversion, however with high sulphur content of about 30 ppm.
Hence the authors suggested optimizing the process parameters to get
better biodiesel yield with lower sulphur content.
Tran et al. (2018) [165] studied the economic potentiality of uti-
lising grease trap waste as the feedstock for biodiesel production via
two routes of with or without the use of acetone as the co-solvent. Even
though the proposed cost of biodiesel produced from grease trap waste
was higher than that of the conventional diesel, this can be improved by
using bio-ethanol as reactant and by modifying the lipid extraction
techniques.
Yellapu et al. (2019) [166] studied the optimization of several
parameters including volume of solvent, temperature, agitation speed
and moisture quantity to improve the oil yield taking freeze-dried scum
as the raw material. The authors reported of obtaining above 90% (w/
w) oil extraction efficiency using both hexane and petroleum diesel as
the organic solvent. The extracted oil was transesterified using an acid
catalyst and obtained an FAME conversion of around 93 and 95% (w/
w) from hexane and petroleum diesel respectively as the co-solvent.
5. Downstream biodiesel processing
Upon transesterification, the resultant downstream mixture is se-
parated into two streams- crude biodiesel stream and glycerol stream.
Crude biodiesel contains impurities in the form of spent catalyst, water,
soaps and salts. Primarily, crude biodiesel is treated with water or
neutralising agent (polyprotic acid) in case of base catalysed transes-
terification in order to neutralise base residues whereas in case of acid
catalysed transesterification polyhydroxy base (NaOH or KOH) is
needed. Another washing step is followed to remove polar compounds
that might be present. Further, biodiesel is vacuum distilled within
certain range of temperature (190–270 °C) in order to meet the speci-
fications decided by ASTM (see Table 6). Vacuum distillation step is
used for methanol recycle before glycerine purification [83]. Ma and
Hanna (1999) [58] reported that the pre-treated ester layer was frac-
tionally distilled at atmospheric pressure or under reduced pressure
(399 Pa) and with 110 KPa of steam in the heating coils. After dis-
tillation C8 and then C10 methyl esters were obtained and accepted as
biodiesel. The residue (C12, C14, C16, saturated and unsaturated C18
fatty acid methyl esters) was sent for further purification process viz.
distillation, crystallization or other processes. Freedman et al. (1984)
[171] reported that the ester layer was purified by dissolving in pet-
roleum ether. To maintain the pH of the mixture at 7, acetic acid or
phosphoric acid was added. Further, it has been washed with water and
dried over anhydrous magnesium sulphate. Further, Solvent has been
removed by evaporation. It was reported [172] that in case of using
homogeneous catalyst there might be some possibility of dissolution of
the catalyst itself in biodiesel layer or glycerine layer. Extensive bubble
washing, spray washing, countercurrent washing, and agitation is used
to wash and purify these contaminated products.
A.P. Bora, et al. Fuel 259 (2020) 116262

Table 6 which has a variety of uses in pharmaceutical, cosmetic, and food in-
Standard specifications for biodiesel ASTM D 6751. dustries [175]. Glycerol stream produced from transesterification, sa-
Properties Method Limits Units Reference ponification and hydrolysis would be highly impure. It comprises of
various impurities such as methanol, glycerol, ash, water, free fatty
Flash point, closed cup D 93 93, min °C [8] acid, unreacted triglycerides, organic and inorganic salts, trimethylene
Phosphorus D 4951 10, max ppm [8]
glycol and matter organic non-glycerol [176–178]. Further, crude gly-
Cetane number D 75 47, min – [167]
Cloud point D 2500 −3 to 12 °C [167]
cerol obtained is often considered a low-value product. Due to low
Kinematic viscosity at D 445 1.9–6 mm2 S-1 [168] purity, it is inappropriate to be used as the feedstock for further ap-
40 °C plication. So, its value can be increased by adopting several purification
Acid number D 664 0.5, max mg KOH g−1 [168] processes viz. conventional filtration, microfiltration, and ultrafiltration
Oxidation stability EN 14,112 3, min h [169]
using organic polymer membranes, simple distillation, vacuum dis-
Sulphated ash D 874 0.02, min wt% [170]
Total sulphur D 5453 0.05, max wt% [170] tillation, chemical and physical treatments, ion-exchange technique and
Total glycerine D 6584 0.240 wt% [83] adsorption [179].
Carbon residue D 4530 0.050, max wt% [83] By considering weight relationship for the hydrolysis reaction (a
Copper strip corrosion at D 130 3, max h [8]
reversible reaction) the triglyceride reacted with water to produce fatty
50 °C
Pour point D 97-05 −15 to °C [170]
acid and glycerol (Scheme 6) [180]. As a purification process of crude
−16 glycerol, distillation step has been used to separate water as well as to
recover methanol due to the difference in their boiling point. Yong et al.
(2001) [181] reported of using vacuum distillation method in order to
5.1. Processing of crude biodiesel stream meet the purification standards (96.6% glycerol). Ion-exchange is an-
other method for the removal of impurities, colour and odour through
Melero et al. (2015) [27] reported that crude biodiesel produced exchanging anion from ion-exchange material [182]. Ooi et al. (2001)
either from primary or secondary sludge composed of unreacted tri- [183] reported that in the purified crude glycerol, by performing the
glycerides, FFA and unsaponifiable fraction such as wax steroids, ter- chemical treatment (acid protonation) at low pH condition could
penoids, esters, and various pharmaceutical chemicals. So, there is an minimize the ash content by using 6% (v/v) sulphuric acid. Kongjao
immediate need for biodiesel purification up to the standard purity (2010) [184] used the combination of the physical and chemical
(> 96 wt%). A preliminary aqueous washing step followed by drying method with addition to the solvent extraction for the treatment pro-
has been applied on the product stream obtained from the in-situ cess and successfully removed ash, water and organic non-glycerol
transesterification. Further, the product was washed with distilled matter. Glycerol is used in pharmaceuticals as a carrier for antibiotics
water (distilled water: reaction production as 2:1) and dried under re- and antiseptics and plasticizers for medicine capsule. It is also used in
duced pressure. After this treatment process, it was observed that the many personal care products as a moisturizing agent. It is used in many
quantity of unsaponifiable matter reduced from 44 to 8% while the food and beverage industry as a softening agent. In the paper industry,
FAME content was raised from 46 to 80%. it is utilized as a plasticizer and in the textile industry; it is used in
Berrios and Skelton (2008) [173] reported biodiesel purification sizing and softening yarn [185].
using Magnasol (magnesium silicate) and compared its efficiency with
the usual washing step by water. As observed that the concentration of
6. Operating parameters and their optimisation for efficient
magnasol greater than 0.75% (w/w) and contact time above 10 min
biodiesel production
were sufficient for removing impurities (except soap and glycerol).
He et al. (2006) [174] used a polysulfone fibre membrane to purify
It is very essential to identify the factors affecting the production of
the crude biodiesel. The crude product was injected through the
biodiesel and their optimisation using various statistical design ap-
membrane which was kept in a water beaker at a temperature of 20 °C.
proaches to maximize the yield. Over the years, researchers working in
Then the filtrate was further placed on a heat source with Na2SO4 (10%
the realm of biodiesel production have established different parameters
w/w) and again filtered. The main objective of using this purification
that play a vital role in affecting the yield. Usually, the acid catalysed
technique was to minimize ester losses. The result was the decreased of
transesterification reaction for the production of biodiesel from sludge
ester losses from 15.2% to 8.1% by using this technique.
is carried out for 24 h in the temperature range of 50–75 °C
[14,17,18,41]. Choi et al. (2014) [121] used xylene as the co-solvent at
5.2. Processing of glycerol stream the reaction parameters of temperature 55 °C, 10 mL g−1 ratio of sludge
to methanol; which accounted a yield of 9.68% (g biodiesel/g dried
The density of glycerol is higher than the esters and therefore can be sludge) in 8 h. Revellame et al. (2010) [14] used the technique of op-
easily separated through gravity settling method. Glycerol, also known timisation of full factorial design approach for the transesterification of
as glycerine, and chemically named as propane-1,2,3-triol, is a chemical activated sludge by in-situ method while varying the temperature at

Scheme 6. The reaction of triglyceride and water.

16
A.P. Bora, et al.
four levels (45–75 °C), methanol to sludge ratio at six levels (5–30, v/w)
and catalyst concentration at five levels (0.5–6 v%). They reported
biodiesel yield of 4.88 w% with numerical and 4.79 ± 0.02 w%, with
experimental optimization technique at the optimum conditions (tem-
perature of 55 °C, methanol to sludge ration of 25:1 and catalyst con-
centration of 4 v% sulphuric acid). They arrived at the conclusion that
owing to the polymerization of unsaturated fatty acids or their esters at
the temperatures above 60 °C the product yield decreases significantly
and indicated the temperature sensitiveness of the reaction.
The most important operating parameters for the synthesis of bio-
diesel from utilizing the sewage sludge as feedstock observed by re-
searchers in the literature are time of reaction, methanol to sludge ratio,
operating temperature, catalyst loading and agitation speed.
6.1. Effect of time of reaction
The effect of reaction time on FAME yield (g FAME/g dried acti-
vated sludge) was investigated by Tran-Nguyen et al. (2015) [145] at
the reaction condition of temperature 250 °C, methanol to dry sludge
ratio of 30 mL g−1 and time 240 min. The FAME yield was found to be
increased with respect to reaction time and passed through a maximum
conversion of 28.98% at 120 min and conversion dropped to 25.70%
when the reaction time was increased to 240 min, owing to the for-
mation of fatty acids by the reverse transesterification [186,187]. The
rate of production of biodiesel was improved by using in-situ transes-
terification for120 min which resulted in a yield of 28.98%, comparable
with the result demonstrated by Huynh et al. (2012) [118] and with
acid catalyzed transesterification [14,17], thus barring more amount of
time of 8 h and 24 h, respectively.
Olkiewicz et al. (2016a) [124] showed the changes occurred on the
FAME yield (based on saponifiable lipid) at different reaction time by
conducting the experiments using optimal parametric values of the
number of sludge lipids, the volume of methanol, amount of ionic liquid
as the catalyst. The reaction rate and the yield of FAME both were in-
tensified with the reaction time up to 5 h and eventually remained
constant. Hence it can be interpreted approximately that the reaction
attained equilibrium after a time period of 5 h, and by increasing the
reaction time to 10 h no appreciable increment in the product yield was
found. The maximum FAME yield of 90% was achieved at the optimum
reaction conditions of 100 °C and 5 h by reacting with lipids (1 g) and
methanol (1 cm3) in the presence of 7% [mimC4SO3H][SO3CF3] ionic
liquid as the catalyst.
Supaporn and Yeom (2016a) [137] also observed the same trend of
increase in the biodiesel yield with increase in reaction time similar to
Tran-Nguyen et al. (2015) [122]. The yield (%, g-biodiesel/g-lipid) of
2.26% was obtained with a reaction time of 4 h which was 1.89% with a
time of 2 h. However, with further increase in time to 6 h the yield
decreased moderately to 2.17%. The decrease in value was attributed to
the reverse transesterification at higher time scales thus resulting in the
loss of esters.
6.2. Effect of methanol to sludge (M/S) ratio on FAME yield
The mass ratio of methanol to biomass is considered as one of the
key parameters affecting the transesterification. As can be seen from the
stoichiometry (Scheme 1), three times of methanol is required for every
mole of triglycerides. Encinar et al. (1999) [188] employed Cynara oil
as the feedstock and reported the optimum value of the molar ratio of
methanol to Cynara oil as 4.05:1 and 5.67:1 respectively, in order to
obtain high FAME yield in the acid catalysed transesterification reac-
tion. The value less than that mentioned resulted in the incompleteness
of reaction leading to the difficulty in glycerol separation from me-
thanol.
Revellame et al. (2011) [18] used dry sludge for the acidic trans-
esterification at 55 °C by employing 25 mL g−1 of M/S ratio with 4%
H2SO4 (v/v) as catalyst loading. The authors reported obtaining 11.38%
17
Fuel 259 (2020) 116262
yield in 2 h while achieving the maximum yield of 35.28% at 24 h.
Although FAME yield (weight basis) was higher in this case with respect
to that obtained with subcritical methanol transesterification at 250 °C,
the latter one achieved the result within a very short reaction time of
2 h. Moreover, subcritical transesterification process being the one
without the presence of catalyst has the advantage of omitting the re-
quirement of separation steps of catalyst from the product mixture
making it environmentally benign.
Tran-Nguyen et al. (2015) [122] varied the M/S ratio from 1:1 to
40:1 mL g−1 to study its effect on the yield of biodiesel at 250 °C and
120 min. The yield increased from 20.17% to 28.98% when the ratio
changed from 1:1 to 30:1 mL g−1. The yield increased with the incre-
ment of methanol dosages and the maximum yield was acquired at the
value of 30 mL of methanol per gram of dry sludge. Because of the
reversibility of the transesterification reaction, surplus amount of me-
thanol is needed to shift the equilibrium to the product side [188,189].
Besides, it can also be interpreted from the kinetic study of transes-
terification and observed by Tran-Nguyen et al. (2015) [122] that more
the ratio between methanol and oil, the greater will be the FAME yield
due to the increased contact between the reactants [190]. But due to the
dilution effect with the usage of more amount of methanol the FAME
yield decreased by 11.61% with the further increase in the ratio of
methanol to 40 mL per gram of dry sludge. Also, higher methanol
loading restrains the separation process between glycerol and FAME
due to the increase in the quantity of glycerol along with the laborious
washing step and impure product quality [187]. The same fashion of
the result was reported by Huynh et al. (2012) [118], which agreed
with the production of lower compounds viz. mono-glyceride, carbo-
hydrate, proteins and pigments with the M/S ratio higher than
30 mL g−1.
Supaporn and Yeom (2016b) [138] studied the lipid transester-
ification for 24 h by varying the methanol dosage in the range of
5–60 mL/g-lipid with the existence of acidic catalyst (0.8% (g/g-lipid)
H2SO4) at 50 °C. The variation of biodiesel yield with the methanol
loading, representing the same trend as reported by Revellame et al.
(2011) [18] and Tran-Nguyen et al. (2015) [122]. The result showed
that an increase of biodiesel yield with the increase of M/S ratio,
achieving the highest yield of 34.8% (g-biodiesel/g-lipid) upon in-
creasing the quantity of methanol from 5 to 20 mL per g of lipid. But the
product yield decreased to 33.6 and 31.7% even after increased in the
methanol dosages to 40 and 160 mL/g-lipid respectively. The optimum
amount of methanol dosage to get the maximum amount of biodiesel
production was identified as 20 mL per gram of lipid. The quantity of
methanol below the optimum value was insufficient in obtaining the
maximum yield whereas higher quantity methanol greater than the
optimum also reduces the biodiesel yield owing to the reduction of
catalytic activity by excess methanol [191].
Olkiewicz et al. (2016a) [124] studied the effect of the solvent
quantity on biodiesel yield corresponding to the M/S ratio of 5:1–35:1.
The experiments were conducted at 40 °C for a reaction time of 1/2 h
with 1 g of sludge lipids by using 7% of the catalyst loading (based on
the mass of lipids). It was observed that the yield of FAME increased to
65% from 44% by increasing the methanol loadings in the range of
0.5–1 cm3 (1 cm3corresponding to 10:1 M ratio approximately), how-
ever, the increasing trend slowed down with further rise in the me-
thanol quantity beyond 2.5 cm3. But, because of the dilution of the
concentration of the ionic liquids (IL) with the increasing amount of
methanol quantity the FAME yield decreased slightly beyond the me-
thanol dosage of 2.5 cm3 which accorded with the previous literature
[192–195]. Moreover, methanol in larger quantity is not favourable for
the recycling of IL for the difficulty of separation of alcohols from it.
Hence, there was a nominal increase in the value of product beyond
1 cm3 of methanol loading and so this value was taken as an optimum
ratio.
A.P. Bora, et al.
6.3. Effect of temperature
The operating temperature of the reaction is also a very significant
factor affecting the biodiesel yield which has been reported by many
authors in literature. It was concluded by Olkiewicz et al. (2015b) [55]
that there was a rise in the number of saponifiable lipids when the
extraction was carried out at low temperatures which were contrary to
the extraction at high temperatures that facilitate the lipids con-
taminated with more non-saponifiable matter resulting in the lower
biodiesel yield. The productivity of the biodiesel remained almost
steady in the temperature range of 40 and 100 °C even though there was
variation in the quantity of extracted lipids including the saponifiable
fractions.
Supaporn and Yeom (2016a) [137] used the reaction parameters:
temperature range of 30–80 °C, methanol to sludge ratio of 10 mL-me-
thanol/g BSS (blended sewage sludge), catalyst loading 0.7% (w/w) of
H2SO4, agitation speed of 150 rpm and 4 h of operating time for the
one-step transesterification. The FAME yield increased from 1.47 to
2.25% when the temperature was raised from 30 to 60 °C. The trans-
esterification rate increases with the temperature since more disruption
of microbial cell walls occurs at high temperature. This increases the
contact area between solvent and lipid which results in the higher yield
of biodiesel [196]. As a result of the minimization of viscosity as well as
improvement of oil solubility the yield of extraction increases with the
temperature [197]. But the plausible product degradation at high
temperatures in conjunction with the vaporization of methanol hinders
the interfacial reaction, lowering the biodiesel yield from 2.25% to
2.13% and 2.10% with the increase in reaction temperature to 70 and
80 °C respectively [198,199].
It was found by Olkiewicz et al. (2016a) [124] that 85% of the
conversion of saponifiable lipids to FAME occurred at 100 °C even
though it was only 43% at the temperature of 25 °C. But the FAME yield
remained almost steady with the continuous rise in temperature from
100 °C to 120 °C, while only 86% of conversion was achieved at 120 °C.
6.4. Effect of catalyst loading
The amount of catalyst dosage/loading in the reaction system plays
a crucial role in the conversion of triglyceride into biodiesel [200].
According to the previous literature many of the researchers used acid
catalysed transesterification and esterification (H2SO4 as a catalyst)
reaction of triglyceride with alcohol for the synthesis of biodiesel. Su-
paporn and Yeom (2016a) [137] used different catalyst concentrations,
viz. 0.1–1.1% (w/w) of H2SO4 for the study of its effect on the reaction
system at the parametric conditions of 70 °C temperature, 150 rpm
agitation speed, 4 h of time and 10 mL-methanol/g-BSS. It was reported
that 2.1% yield was obtained with 0.7% catalyst dosage while 1.4% was
obtained with 0.1% dosage. Hence the analysis interpreted that the
yield increased with the catalyst dosage owing to the vigorous con-
tacting as a result of high contact surface [201].
Olkiewicz et al. (2016a) [124] studied the activity of [mimC4SO3H]
[SO3CF3] catalyst on the conversion of triglyceride into FAME at dif-
ferent catalyst loading of 3% to 12% by keeping fixed the other reaction
conditions (temperature 40 °C, reaction time 30 min) with 1 cm3 vo-
lume of methanol per gram of extracted lipid. The higher yield is at-
tributed by the retention of the sulfonic acid group (–SO3H) in pro-
portion with the order of the reaction. The reported increase in
biodiesel yield was from 49% to 65% with the increasing catalyst do-
sage from 3% to 7% (w/w) but remained almost steady with further
increase in it.
Supaporn and Yeom (2016b) [138] also agreed with the previous
literature that by increasing the catalyst dosage the FAME yield in-
creased considerably. The results showed a significant increase of yield
from 32.2 to 38.7% with the increase in catalyst dosage from 0.1 to
0.2%. It was observed by them that the further increase in catalyst
dosage beyond 0.2% resulted in a decrease of biodiesel yield primarily
18
Fuel 259 (2020) 116262
because of the polymerization of the unsaturated fatty acids in the
existence of surplus acid, higher operating temperature and time [202].
6.5. Effect of agitation speed
The effect of agitation speed on the production of FAME was in-
vestigated by Supaporn and Yeom (2016a) [137] varying it in the range
between 150 and 900 rpm using 10 mL-methanol/g-BSS and 0.7% (w/
w) of H2SO4 at 60 °C and 4 h of reaction time. The increase in agitation
speed above 300 rpm did not exhibit any considerable increase in the
product yield as it accomplished in the range of 150–300 rpm by in-
creasing the yield from 2.25% to 3.1%. This trend of the result may be
possible because of the leaching of the catalyst in the reaction mixture
developed by the high shear stress originated from the high agitation
speed. The agitation speed not only promoted the mixing intensity of
hydrophobic lipids with the catalyst-methanol mixture but also main-
tains the temperature uniformity in the reaction system [203]. Ad-
ditionally, it also increased the interfacial contact area between the
reactants ensuring the adequate exposure of biomass to the methanol
[204].
7. Reaction kinetics
The study of the kinetics and mechanisms of the transesterification
reaction is very essential to develop and design the process for better
biodiesel productivity. The kinetic data provides valuable input for
reactor design, scale up and optimisation of the process, control of the
process, development of the efficient catalyst and lastly economic fea-
sibility analysis for industrial implementation. Therefore the determi-
nation of kinetic model is very crucial to predict the transesterification
rate equation under various parametric conditions along with the
consideration of other important factors like mixing pattern and dy-
namics of the reactor fluid. Although, kinetic modelling studies of
transesterification of vegetable oils using homogenous and hetero-
geneous catalysis were attempted by many researchers [205], only a
few studies have been reported for the case of sewage sludge derived
biodiesel/bio-oil.
Mondala et al. (2009) [17] reported primarily two major assump-
tions in the kinetic data analysis. The first one was that lipids derived
from the primary sludge are a combination of triglycerides, diglycerides
and monoglycerides but for simplicity of the kinetic data analysis, it
was assumed that majority of the portion composed mostly of trigly-
cerides. Further, it was assumed that the concentration of methanol
remained constant over the experiment because it is present in plenty
with respect to the triglycerides in the sludge resulting in a pseudo
reaction rate constant. Further integral method was performed on the
conversion versus reaction time data and obtained a pseudo-second
order kinetics. Linear regression technique was used for the determi-
nation of pseudo reaction rate constants and their corresponding coef-
ficients of regression (R2). It was justified that only the amount of the
acid catalyst significantly affects the pseudo reaction velocity constant.
From the analysis of the rate constant data for in-situ transester-
ification of primary sludge provided by Mondala et al. (2009) [17], the
values of activation energy were calculated by the present authors using
the four sets of data and given in Table 7. From the analysis, it can be
interpreted that the higher activation energy was needed for the cata-
lyst dosage of 1%v where around half the energy was needed while
increasing the catalyst dosage to 5%v. whereas there was no significant
effect for the increased of methanol to sludge ratio in the requirement
of activation energy. Hence it can be interpreted that the catalyst
played a vital role in the transesterification reaction.
Mondala et al. (2012) [206] studied the kinetics of three routes of
the aerobic fermentation process which included non-lipid biomass
synthesis, lipid accumulation and utilization of glucose by sludge mi-
croorganisms. The Logistic equation derived from the Monod equation
was used to characterize the rate of non-lipid biomass synthesis which
A.P. Bora, et al. Fuel 259 (2020) 116262

Table 7 of energy for the combustion of heavy fractions of bio-oils.

Calculation of activation energy from the data provided by Mondala et al., 2009
[17]
Temperature (°C) H2SO4Concentration Methanol
(v %) to Sludge
ratio
(molar
basis)
50 1 8:1
75 1 8:1
50 1 12:1
75 1 12:1
50 5 8:1
75 5 8:1
50 5 12:1
75 5 12:1
represented the growth in terms of carrying capacity of the culture
medium. Luedeking-Piret equation was used to represent the rate of
lipid accumulation. The equation represented the relationship between
rate of lipid production with the instantaneous non-lipid biomass con-
centration and the growth rate of the non-lipid biomass. The utilization
of glucose by the activated sludge microorganisms was also presented
by using the kinetic model of Luedeking-Piret equation which re-
presented the utilization of glucose as a function of the instantaneous
growth of non-lipid biomass, formation rate of lipid and a coefficient of
cell maintenance. These kinetic model equations are presented in
Table 8. The analysis of the data from the mathematical models de-
picted a significant correlation with the experimental results. Analysis
of the kinetic data revealed that the production of lipid in the activated
sludge was a mixed growth phenomenon coupled with the overall
biomass production. As a result to optimize the process of aerobic fer-
mentation it is required to consider the yields of non lipid biomass
along with the gravimetric yields of lipids.
Leng et al. (2018b) [153] used the Ozawa-Flynn-Wall kinetic
equation to calculate the activation energy which is based on the as-
sumption that the rate of reaction is a sole function of temperature at a
constant conversion value. The graph of conversion rate vs. tempera-
ture depicted a wide combustion range of temperature for the bio-oils.
It was accounted that the approximately 30% of the bio-oils were
combusted at temperature more than 600 K regardless of the heating
rate. At conversion rate between 70 and 80% the decomposition tem-
peratures of the bio-oils were in close proximity except for some heavy
fractions. The reported graphical data of activation energy (Ea) with the
conversion rate reveals the rise of activation energies of the bio-oils
with the increase in conversion rate, but it decreased after the attain-
ment of maximal value. The highest values of Ea were obtained at
higher conversion rate, which interpreted the requirement of high input
Patiño et al. (2018) [47] reported kinetic data analysis based on
with or without the presence of sonication and found better results
Rate Activation under sonicated conditions. It was reported that in-situ transester-
constant Energy (kJ/ ification was mass transfer controlled. Under the assumption of mass
(K) (L/ kmol) transfer dominance and employing unsteady state mass transfer ana-
mol.h)
lysis in a stirred batch reactor, a first-order expression for the con-
centration of triglyceride in the solid phase was derived. Under the
3.0111 4.565 derivation, it has been assumed that in the liquid phase the con-
3.4023 centration of triglycerides is negligible. Without pre-treatment, the
3.1044 4.649 overall yield was considerably lower than that with ultrasound as pre-
3.5156 treatment at any given time. It was found that the behaviour of the
4.2471 2.332 yield curve was asymptotic both in the presence and absence of ultra-
4.5206 sonic pre-treatment. It has been reported that the total yield of FAME
4.3487 2.352 obtained was around 4 g corresponding to 100 g of dry sludge. The
4.6312 fitting of experimental data was performed to evaluate the solid-liquid
mass transfer coefficient (ksL) for reaction with and without ultrasonic
pre-treatment. The ultrasonic pre-treatment enhanced the solid-liquid
mass transfer coefficient by 3.2 times when compared with the case of
no pre-treatment. This might have contributed for better yields of FAME
in case of ultrasonic pre-treated reaction since the reaction was estab-
lished to be mass transfer limited.
Systematic studies on the rate controlling step in the production of
biodiesel from sewage sludge are required to be carried out, which
would be helpful in converting the laboratory information to the
commercial scale production.
8. Biodiesel quality
The biodiesel to be available for the commercial usage has to go
through the standard specification ASTM D 6751 (Table 6) and EN
14214 (Table 9) standards for biodiesel respectively so that it can be
utilised efficiently in the engine without any hardware modifications. It
is quite challenging for the researchers to guarantee the quality of
biodiesel synthesised from the lipids extracted from wastewater sludge.
The sludge contains various chemicals like wax esters, steroids, terpe-
noids, polyhydroxy alkanoates, hydrocarbons, linear alkyl benzene,
polycyclic aromatic hydrocarbons and pharmaceutical chemicals along
with different lipids sources like triglyceride, fatty acids, phospholipids
and bacterial lipids [14,23,44,208,209]. There is plenty of possibility of
extraction of these chemical compounds in addition to the lipids which
could alter the gravimetric yield of biodiesel. The usage of the cracking
process could convert these contaminants and significantly increase the
FAME yield from the wastewater sludge [14,210,211].
It was observed by Dufreche et al. (2007) [41] that the extraction
with SC-CO2 upon the addition of methanol exhibited a lower quantity
of unsaturated fatty acids. The author reported that the hexane ex-
tracted a higher quantity of unsaturated fatty acid in comparison to the
methanol. However, the C16 unsaturated fatty acids were an exception

Table 8
Kinetic model reported in the previous literature [153,206].
S No. Equation Expression Description

1 Logistic equation X: non lipid biomass concentration at time t (h), g L−1

dX
dt
= μmax X (t ) 1 − ( X (t )
Xmax ) µmax: maximum specific growth rate, h−1
Xmax: maximum non lipid biomass concentration corresponding to the maximum carrying capacity, g L−1
2 Luedeking–Piret dP
= nX + m
dX P: lipid concentration at time t (h), g L−1
dt dt m, n: empirical constants
3 Luedeking–Piret −
dS
=
1 dX
+
1 dP
+ ke X S: residual glucose concentration at time t (h), g L−1
dt YX / S dt YP / S dt YX/S : non lipid biomass coefficient
YP/S: lipid yield coefficient
Ke: maintenance coefficient
4 Ozawa-Flynn-Wall logβ = log
AEa
− 2.315 − 0.457
Ea g(α): a function of conversion degree α, where
g (α ) R RT Wo − W
α= W , W and W∞ are initial, instantaneous and final weights in the thermo gravimetric analysis
W0 − W∞ o
β: heating rate

19
A.P. Bora, et al. Fuel 259 (2020) 116262

Table 9 the raw material showed that the majority components were C14, C16
EN 14214 standard for biodiesel [207]. and C18 but with considerable variation in the weight percentages.
Property specification Units Test method Limits However, unlike the biodiesel derived from primary and secondary
sludge, the scum derived biodiesel accounted for oleic acid as the major
Flash point °C EN ISO 3679 101, min component.
Cetane number – EN ISO 5165 51, min
However, the scum derived biodiesel contains a much higher
Density at 15 °C kg/m3 EN ISO 3675/12185 860–900
Kinematic viscosity at 40 °C mm2/s EN ISO 3104 3.5–5
quantity of saturated fatty acids than that derived from the refined
Acid number mg KOH/g EN 14104 0.5, max vegetable oils [157]. The higher amount of saturated fatty acid in the
Oxidation stability – EN 14112 3 h, min fuel accounted to the higher cetane number which enhances its com-
Carbon residue % m/m EN ISO 10370 0.3, max bustion characteristics but on the contrary, it leads to the increase in the
Sulphated ash content %mass EN ISO 3987 0.02, max
cloud number which adversely affects the engine in the cold weather.
Monoglycerides %mass EN 14105 0.8, max
Diglycerides %mass EN 14105 0.2, max The biodiesel derived from scum sludge meets the quality specification
Triglycerides %mass EN 14106 0.2, max suggested by ASTM and EN regulations excluding some of the proper-
Free glycerine %mass EN 1405/14016 0.02, max ties like sulphur content, total acid number and oxidation stability. As
Total glycerine %mass EN 14105 0.25
reported by Ma et al. (2016) [214] the sulphur content of scum was
Phosphorus %mass EN 14107 0.001, max
Total contamination mg/kg EN 12662 24
found to vary in the range of 600–1000 ppm which was way above the
permissible limit by ASTM specifications. As specified by ASTM D 6751
the permissible limit for sulphur content in the biodiesel is less than
in that case. The comparison of sludge fatty acid profile with the profile 15 ppm. In the previous study as reported by Bi et al. (2015) [157], the
of standard soybean oil showed that the concentration of saturated fatty sulphur content, found to be around 33 ppm, which was twice the
acids in the sewage sludge samples was higher than that of standard permissible limit of ASTM specifications. Hence process modification
soybean oil. Even though the larger quantity of saturated fatty acids in that ensures lower emissions of sulphur is to be done to utilise the scum
the fuel could create difficulties in the cold weather condition due to derived biodiesel as a potential source of energy along with the other
gelling, it produces a better-quality burning fuel [212]. sources of biodiesel.
Analysing the FAME distribution reported by different researchers
in literature, it can be stated that the esters of acids with C16 and C18 9. Process economy
dominates the profile regardless of the fraction studied [14,17,52,54].
Palmitic (C16:0), palmitoleic (C16:1), stearic (C18:0) and oleic acids The renewable source derived biodiesel has many environmental
(C18:1) are the main identified fatty acids with the main fraction benefits making it a potential alternative fuel. Indeed, the main draw-
containing below 3% of other polyunsaturated fatty acids. As the ve- back that lies in the path of commercialization is its cost and non-
getable oil derived biodiesels has poor autoxidation quality it leads to availability in plentiful amount. The cost of raw materials and proces-
the decrease in the oxidative stability of the product, the wastewater sing cost principally contribute to the production cost of biodiesel in-
derived biodiesel is preferable [213]. hibiting its commercial growth against the conventional diesel
The gas chromatography analysis of the fatty acid profile obtained [14,215].
from both the types of sludge source was found to be in close proximity, Being a waste to be treated before disposal, municipal sewage
as demonstrated by Mondala et al. (2009) [17]. They reported that both sludge (MSS) if utilized as raw material, aids in significantly lowering
the biodiesel sample from primary and secondary sludge contained the production cost of bio-fuel. Organic solvents can be used for lipid
methyl esters of palmitic acid, stearic acid and oleic acid. However, the extraction from MSS to produce biodiesel. The solvents can, however,
secondary sludge derived biodiesel contained a significantly higher be recovered and the amount of solvents which can be recovered is
amount of palmitoleic acid than that of primary sludge derived bio- almost 99% [25]. According to the survey in 2010 the estimated pro-
diesel. duction cost of biodiesel was USD 3.11 to USD 3.23 per gallon using
Comparison of fatty acid profiles for anaerobic-anoxic-oxic (A2/O) primary and secondary sludge as feedstock as compared to USD 4.00 to
and membrane bioreactor (MBR) sludge studied by Qi et al. (2016) USD 4.50 per gallon for biodiesel obtained from refined soy oil and USD
[140] reported the higher quantity of saturated fatty acid viz. palmitic 3.00 per gallon for commercial diesel [17,25,41,216].
acid and stearic acid in the A2/O sludge in comparison to the MBR An economic analysis was reported by Pokoo-Aikins et al. (2010)
sludge. Whereas, on the contrary, MBR sludge contained a higher [25] where different solvents like toluene, hexane, methanol and
number of unsaturated fatty acid viz. palmitoleic acid and oleic acid. As ethanol were used for the purpose of lipid extraction. The raw material
observed by the authors this dissimilarity was owing to the original was assumed to be inexpensive while the drying cost was considered
fatty acid composition of the sludges. under the wastewater treatment plant during the economic analysis.
Yi et al. (2016) [163] showed that the composition of FAME ex- Among the four solvents used toluene and hexane were found to be
tensively depends on the types of sludges (scum, primary and sec- least costly with the expenses of 2.79 and 2.89 $/gal respectively. Even
ondary) rather than the co-solvents used for extraction and constituted though toluene is less expensive but the recovery process consumes
a major quantity of palmitic acid and oleic acid. The primary sludge high input because of its high boiling properties.
contained a higher quantity of palmitic acid in comparison to the sec- The process proposed in the following paper was comparable to the
ondary and scum sludge. Whereas oleic acid was the major component process depicted by Pokoo-Aikins et al. (2010) [25], and avoids any
in the FAME produced from the scum sludge. expensive operations of drying and also directly uses dewatered sludge.
Patiño et al. (2018) [47] also observed the dominance of C16 and Mahamuni and Adewuyi (2009) [217] reported that the utilization of
C18 fractions in the fatty acid distribution profile for both the solid- ultrasound at high frequency would significantly reduce the cost of
liquid and liquid-liquid methods. The fatty acid profile for anaerobic production of biodiesel. The primary reason behind this was that the
sludge contained higher a number of saturated compounds which was use of cavitational reactors significantly minimizes the requirement of
contrary to the case of other types of sludges viz. oxic sludge, anoxic alcohol involved in the reaction along with the higher conversion that
sludge and floating sludge. This was accordingly with the ease of con- could be achieved within a short span of time with the application of
version of saturated lipids into FAME due to its enhanced saponifiable low energy input. It can be said that by keeping aside the economic
quality. consideration, another aspect has to be taken into account which is the
The GC analysis of the biodiesel obtained from the scum sludge as specific energy demand (SED) i.e. the amount of energy input to pro-
duce 1 kg of FAME. This parameter can be considered as a real

20
A.P. Bora, et al. Fuel 259 (2020) 116262

Table 10
The primary challenges in the path of commercialization of biodiesel production.
Sl. No. Primary factors Explanation

1. Sludge collection Collection of sludge from various waste water treatment plant and their pre-treatments
2. Drying operations Drying of large amount of from the sludge is associated with high cost along with filtration and centrifugation
3. Extraction of lipids Requirement of large volume of organic solvents which are expensive, modification of the extraction technique to maximize the
solvent selectivity
4. Microbial processing Separation of pharmaceutical chemicals, metallic compounds from the sludge
5. Production of biodiesel and its The simultaneous extraction and acid transesterification increases the efficiency of biodiesel production, the formation of soap as
purification the by-product of the reaction creating difficulties in product separation along with the separation of glycerol. Intensify the
biodiesel production method using ultrasound or microwave heating to maximize the yield within a short span of time
6. Product quality Improving the biodiesel quality as per the ASTM standards
7 Designing of reactors The efficient biodiesel production is dependent on the design of type of bioreactors used, continuous reactor is more preferable
8 Economic viability The production cost of the biodiesel should be below the cost of commercially available petro diesel

convenience to characterize the biodiesel production process.
Pastore et al. (2013) [45] calculated a SED of 205 MJ/(kgFAME) and
140 MJ/(kgFAME) respectively for alcoholysis of dry sludge and dewa-
tered sludge. The SED of 44 MJ/(kgFAME) was obtained for the process
of methanolysis of dewatered acidified sludge. The yield of FAME was
kept constant while calculating the required input of SED for 80% water
containing dewatered sludge. However, for dewatered sludge con-
taining 85% water required the SED of 250 MJ/(kgFAME) for alcoholysis
of dry sludge, 187 MJ/(kgFAME) for alcoholysis of dewatered sludge and
60 MJ/(kgFAME) for the two-step process.
In another study, Olkiewicz et al. (2016b) [218] evaluated the op-
timised break-even point (BEP) for biodiesel production from primary
sludge to be 1232 $/t. As estimated by the International Energy Agency
(IEA) in 2016 the price of fossil fuel in Europe was 1376 $/t on January
2016, relatively higher than the biodiesel. Hence utilization of sewage
sludge for the synthesis of biodiesel could compete with the other
sources and has the prowess to be used as an alternative energy source.
Although extensive research is being carried out on the biodiesel ob-
tained from microalgae, its commercialization is not feasible till yet or
it can be said that its commercial viability is not possible till now [219].
Different authors calculated the BEP of microalgae-derived biodiesel at
different conditions viz. 1344 $/t for best conditions, 2953 $/t for mi-
croalgae obtained from open ponds and 5700 $/t for an comprehensive
study [219–221]. It is worth noting that these BEP values are higher
than the one estimated for sewage sludge biodiesel. The main ad-
vantage of sewage sludge over other feedstock was its availability at
almost free of cost or minimal cost. On the other hand, in the case of
biodiesel produced from microalgae, the total production cost con-
stitutes 65% of the biomass production cost [219].
The breakeven selling price of bio-fuel ($0.49/L) estimated by Xin
et al. (2018) [222] was comparable to the result obtained by Orfield
et al. (2014) [223]. Xin et al. (2018) [222] concluded that it requires
less than $0.55/L to produce bio-oil from algae to be competent with
the production cost of conventional commercial fuel oil at $80 per
barrel. Although this estimated calculation was lower than the centrate-
originated bio-fuel production from algae at $0.59/L, Xin et al. (2016)
[224] established the integrated system to be superior to the separated
system. Fraia et al. (2016) [225] reported the 6.8 years as the simple
payback period of the cogeneration system for sewage sludge treat-
ment. The study also expressed the simple payback period of integrated
wastewater bio-fuel system to be around 9.05 yrs, 8.08 yrs and 7.47 yrs
for crude oil equivalent prices of $74.14, $80.43 and $85.15, respec-
tively. The estimated cost of production of oil via pyrolysis of sludge
was 6.9 ¢/kg-ds (digested sludge) which were in good agreement with
the result obtained by Kim and Parker (2008) [226].
The consensus can be stated from the economic analysis that the
utilization of MSS for biofuel production can minimize the environ-
mental hazard and has the potentiality to become remunerative.
10. Perspective and concluding remarks
Bio-fuels (Biodiesel and Bio-oil) are considered as the major re-
newable sources of energy today which have many advantages over
conventional fossil-derived fuel. However, the high production cost
owing to the high cost associated with the feedstock has made it un-
economical contrasted to fossil-derived fuel. In addition, the currently
used raw materials such as vegetable oils and animal fats are conflicting
with the human feedstock facilitating to the higher cost of bio-fuel.
On the other hand, the readily and inexpensively available MSS can
be accounted as an alternate and inherent feedstock for bio-fuel
synthesis because of its lipid content. Since the sludge contains an
adequate amount of lipid content it can be transformed into FAME
primarily by acid catalysed transesterification or converted to bio-oil by
the use of pyrolysis. However, the high water content of the sludge is a
major hurdle for producing biodiesel via this route in a commercially
viable manner. Starting with the collection of the raw sludge to its pre-
treatment, and dewatering to drying of sludge are expensive processes
with the current technological know-how.
Firstly, the usual drying methods are both expensive and ineffective
for lipid recovery which makes the process of biodiesel production from
MSS economically not feasible. Hence, proper care must be exercised in
scaling up this process so that there is a cost-effective drying method to
evaporate the water from the sludge. It is recommended to use vacuum
drying instead of freeze drying as it is capable of minimizing the overall
biodiesel cost due to its high efficiency.
Secondly, the lipid extraction step which primarily depends on the
raw sludge source and its type, requires a significant amount of organic
solvents and henceforth increasing the production cost of biodiesel. The
significant parameters affecting the process of lipid extraction are
identified as solvent selectivity, the ratio of solvent to dry sludge, time
of extraction, reaction temperature and recycling of solvent. These
parameters need to be optimized with the use of modern optimisation
techniques to maximize lipid extraction. Although the use of super-
critical CO2 resulted in a better yield of lipid than the single organic
solvent it is not economically feasible owing to its high processing cost.
The modern process intensification (PI) techniques such as ultrasound
and microwave-assisted extraction have a better scope in the coming
future. Only a few papers have been reported about the application of
these new PI tools for lipid extraction from MSS, where several ad-
vantages such as the short requirement of process time and lower op-
erating cost were highlighted. Moreover, the focus must be given to the
alternate solution for the elimination of those costly and harmful or-
ganic solvents for the extraction purpose. Instead, green extraction
technique using water as a solvent could be used.
Lastly, the methods of biodiesel synthesis are not competitive with
the currently existing conventional diesel-producing technology.
Heterogeneous catalysis is more efficient and economical compared
with the homogeneous catalysis, with benefits like (i) less processing
steps for product separation and purification (ii) more amounts of
glycerol production and (iii) ease of catalyst recovery. Moreover, the

21
A.P. Bora, et al.
prowess of acid heterogeneous catalyst to convert lipids of high FFA
content extracted from cheap feedstock establishes its economic feasi-
bility. Utilising the acid heterogeneous catalysis for the synthesis of bio-
fuel from high FFA containing sewage sludge feedstock is a potential
alternative. Although the transesterification reaction in the presence of
an acid heterogeneous catalyst is slow, the modern intensification
techniques like ultrasound and microwave irradiation could be em-
ployed to enhance the process. The different challenges occurring in the
path of biodiesel production are summarised in Table 10.
The optimisation of different parameters involved in the process of
bio-oil production also needs to be addressed to produce high-quality
bio-oil and chemicals. The focus should be given to the up-gradation
technique like emulsification and micro-emulsification to increase the
fuel characteristics of bio-oil or it’s blending with biodiesel to enhance
the combustion quality with better emission properties.
Finally, the fundamental kinetic mechanism studies should be per-
formed for a better insight into the catalytic behaviour for the pro-
duction of both biodiesel and bio-oil from MSS in order to enhance its
productivity.
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