Journal of Environmental Management xxx (2017) 1e7

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Journal of Environmental Management

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Research article

Feedstock and process influence on biodiesel produced from waste

sewage sludge
Andrea G. Capodaglio a, *, Arianna Callegari a
a
Department of Civil Engineering & Architecture, University of Pavia, Pavia, 27100, Italy

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

Article history: Disposal of sewage sludge is one of the most important issues in wastewater treatment throughout
Received 25 January 2017 Europe, as EU sludge production, estimated at 9.5 million tons dry weight in 2005, is expected to
Received in revised form approach 13 million tons in 2020. While sludge disposal costs may constitute 30e50% of the total
15 March 2017
operation costs of wastewater treatment processes, waste sewage sludge still contains resources that
Accepted 28 March 2017
Available online xxx
may be put to use, like nutrients and energy, that can be recovered through a variety of approaches.
Research has shown that waste sewage sludge can be a valuable and very productive feedstock for
biodiesel generation, containing lipids (the fats from which biofuels are extracted) in amounts that
Keywords:
Wastewater sludge
would require large areas cultivated with typical biodiesel feedstock, to produce, and at a much lower
Feed stock properties final cost. Several methods have been tested for the production of biodiesel from sewage sludge. To date,
Biodiesel among the most efficient such process is pyrolysis, and in particular Microwave-Assisted Pyrolysis (MAP),
Pyrolysis under which process conditions are more favorable in energetic and economic terms. Sludge charac-
Microwaves teristics are very variable, depending on the characteristics of the wastewater-generating service area
and on the wastewater treatment process itself. Each sludge can be considered a unique case, and as such
experimental determination of the optimal biodiesel yields must be conducted on a case-by-case basis. In
addition to biodiesel, other pyrolysis products can add to the energetic yield of the process (and not
only). This paper discusses how feedstock properties and process characteristics may influence biodiesel
(and other products) yield from pyrolytic (and in particular, MAP) processes, and discusses future
possible technological developments.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction through a variety of approaches.

Safe disposal of sewage sludge is one of the most important
issues in the wastewater treatment cycle: at the European Union
level, the 2005 sludge production was estimated in 9.5 million tons
dry weight, up more than 54% in ten years, expected to reach
12.9 Mt by year 2020, a further increase of more than 30% (David
et al., 2008). Sludge disposal costs may constitute up, and some-
times above 50% of the total cost of operation of an urban waste-
water treatment plant, and include common disposal options like:
landfilling, disposal in agriculture (about 40% EU-wide), incinera-
tion or co-incineration, use in industrial production of bricks, as-
phalts, concrete. Sewage sludge, however, still contains beneficial
resources such as nutrients, that can be recovered through specific
processes (e.g. precipitation as struvite) and energy, recoverable
* Corresponding author.
E-mail address: capo@unipv.it (A.G. Capodaglio).
On the other hand, to reduce fossil fuels consumption and car-
bon emissions, energy industry and government policies world-
wide are promoting the use of biodiesel and other non-petroleum
biofuels. The current European Union (EU) commitment under
Directive 2003/30/EC on the promotion of biofuels for transport,
sets a target of 5.75% of all transport fuels by 2010, increased to 10%
by 2020 by the recent European Commission energy roadmap
(Raboni et al., 2015). Based on life cycle analysis (LCA), it has been
estimated that replacement of petroleum-derived diesel fuel with
biodiesel would reduce greenhouse gas emission by up to 45% due
to the carbon neutrality of the latter (Basha et al., 2009).
A “biofuel” is defined as a fuel that is produced through
contemporary biological processes, rather than by geological ones,
such as those involved in the formation of fossil fuels. An ongoing
debate on biofuels sustainability has emerged since the biofuels
industry gathered momentum. While 1st generation biofuels were
(and are) mainly produced with feedstock with food value for

http://dx.doi.org/10.1016/j.jenvman.2017.03.089
0301-4797/© 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Capodaglio, A.G., Callegari, A., Feedstock and process influence on biodiesel produced from waste sewage
sludge, Journal of Environmental Management (2017), http://dx.doi.org/10.1016/j.jenvman.2017.03.089
2 A.G. Capodaglio, A. Callegari / Journal of Environmental Management xxx (2017) 1e7
humans or animals, 2nd generation biofuels are increasingly being
produced from lignocellulosic and waste materials and could
enable far greater reductions in greenhouse gases (GHG) emission
(Capodaglio et al., 2016a). In 2009, biodiesel represented about 75%
of total biofuels produced in the EU. If produced to comply with
ASTM D6751 (the international standard of biofuels), it can be used
for transportation and industrial purposes, and represents a valid
alternative to conventional diesel because is renewable, biode-
gradable, less toxic, and has low emission profiles. With a similar
energy density to diesel, it can be used directly without any vehicle
or engine modification, and does not require a new type of refu-
eling infrastructure. For these reasons, the production of biodiesel
in the EU has increased from 3.6 billion liters in 2005 to 10.7 billion
liters in 2010 (EDB, 2015; Thevenieau and Nicaud, 2013), initially
from feedstocks such as soybean, canola, rapeseed, sunflower,
palm, and coconut oils. Still, biodiesel production is currently
limited due to high raw material costs, lack of agricultural lands and
perceived conflict and impact on food prices. The search for cheaper
feedstocks has turned towards various forms of waste, alternative
raw materials, including waste animal fats, cooking oils (Bhatti
et al., 2008; Hossain and Mekhled, 2010; Wallace et al., 2016) and
lipids in sewage sludge (Dufreche et al., 2007; Zhang et al., 2014a).
Kwon et al. (2012) showed that sewage sludge could produce sig-
nificant amounts of lipids at low cost, with high yields of fatty acids
methyl esters (FAMEs), which are the main ingredients of the fuel.
Traditionally, sewage sludge has been processed for decades in
anaerobic tanks to produce biogas, a mixture of CH4 and CO2 that
can be used as such or further refined to obtain bio-methane, a
renewable fuel with characteristics practically identical to those of
fossil methane (Zhang et al., 2014b; Capodaglio et al., 2016b).
However, recent work has demonstrated that the production of
biodiesel using the lipids extracted from sewage sludge could be
economically feasible because of the remarkably high yield of oil
and low cost of this feedstock (wastewater sludge can be consid-
ered “free”, except for transportation costs), as compared to con-
ventional biodiesel feedstocks (Siddiquee and Rohani, 2011).
The purpose of the study, having already demonstrated the
possibility of recovering biodiesel from waste sludge materials by
microwave-assisted pyrolysis (MAP) process (Xie et al., 2014;
Capodaglio et al., 2016c), is to attempt a more encompassing
analysis of the process itself, in order to define its outcome limits
and overall sustainability. In a previous experimental study
(Capodaglio et al., 2016c), the authors concentrated on the sludge
oil production potential by MAP, showing that under specific cir-
cumstances the process itself can be energetically positive, but
contributions of generated syngas and char were totally neglected.
These products can bring additional value to the process. Re-
lationships between feedstock properties, process characteristics
and products yields are further assessed in this work.
1.1. Waste urban sludge as a biodiesel feedstock
Feedstock selection is one of the most important aspects that
should be taken into account, determining the economics of the
entire biodiesel (and other resources) recovery process. As a gen-
eral rule, in every production line, feedstock price should not be
more than 50% of the production cost. Until recently, it was esti-
mated that oils used as feedstock claimed about 80% of production
costs: for this reason, many researchers believe that waste sludge
has ideal characteristics for a basic biodiesel feedstock (Van Gerpen,
2004). Unlike other common feedstocks used for biodiesel pro-
duction (food and non-food crops) which prices may experience
severe fluctuations due to market conditions and competition with
other uses, sludge is a waste product, abundantly produced in large
quantities at an almost constant rate during the year,
Please cite this article in press as: Capodaglio, A.G., Callegari, A., Feedstock and process influence on biodiesel produced from waste sewage
sludge, Journal of Environmental Management (2017), http://dx.doi.org/10.1016/j.jenvman.2017.03.089
uncompetitive with the food market, and readily available.
Currently, biodiesel diffusion is limited mostly by high raw
material costs. Since waste sludge, generally, can be considered cost
free (or even associated with a “gate fee” for its processing) and
could be made by up to 30% (by weight) lipid fraction (Dufreche
et al., 2007), which could then be processed into FAMEs, it could
form an unexploited and almost endless source of cheap and
readily available feedstock for biodiesel production.
Sewage Sludge contains a variety of organic and inorganic
compounds originally contained in wastewater. The composition of
sludge collected in primary sedimentation basins (primary sludge)
consists to a high degree of undegraded organic matters. Secondary
sludge, resulting from the interaction of microorganisms with
organic matter in a process called activated sludge, exists normally
in form of flocs, which besides living and dead biomass contain
organic and mineral parts. Organic materials present in the waste
water are detergents, pesticides, fats, oil and grease, colorings,
solvents, phenols etc. Digested sludge is a mixture of primary and
secondary sludge treated in an anoxic reactor to stabilize (reduce)
its organic content, often with recovery of “biogas” (a mix of
methane and CO2 gases with other impurities). Less frequently,
sludge can be stabilized aerobically, although this process is quite
expensive and energetically disadvantageous. It has been claimed
that the yield of FAMEs from primary sludge is greater than that of
activated sludge. Lipid extraction from raw sludge would require
large amounts of organic solvents in stirred and heated vessels.
Dewatered sludge (solids content 10e20%) is denser and hinders
lipid extraction, however, lipid extraction from dried sludge (solids
content above 35%) is feasible, after adequate pretreatment
(centrifugation and/or filtration processes) to obtain the proper
humidity content.
Average characteristics and yields of different sludge types re-
ported in literature are shown in Table 1. The wide lipid yields for
primary sludges will depend on plant configuration, i.e. on mixing
of recovered floating oil and grease with the primary sludge. Such
configuration choices would have a significant effect on lipid yield.
1.2. Technologies for biodiesel production from waste sludges
Two main technologies are nowadays used for biodiesel pro-
duction from wastewater sludge: lipid transesterification and py-
rolysis. Several other technological processes have been studied
and applied for biodiesel production from sludge and other feed-
stocks. Biodiesel consists of FAMEs, when methanol is the alcohol
used in the transesterification process of lipids, or fatty acid alkyl
esters (FAAEs) when produced via base-and/or-acid-catalyzed
transesterification. In a typical process, triglycerides with low free
fatty acid (FFA) (less than 0.5%) content are transesterified with
methanol (MeOH) in the presence of alkaline homogeneous cata-
lyst such as potassium hydroxide (Kwon et al., 2013).
Alternative approaches for dealing directly with dewatered
sludge while minimizing the energy requirement of the entire
process have been investigated: (i) direct methanolysis and (ii)
preliminary extraction with hexane of the lipidic fraction and
subsequent methanolysis into FAMEs (Pastore et al., 2013). Bio-
diesel yields from lipids extracted by different methods, i.e. acid
hydrolysis, Soxhlet method, and water bath shaking method differ
considerably: in a study by Zhu et al. (2014) they were 1.33, 6.73,
and 4.92% (dry weight), with purity values, determined by GC
MS,
of 97.5, 94.3, and 83.3%, respectively. Optimum production of bio-
diesel is faced with considerable challenges as lipids are extracted
and then transesterified. In situ transesterification procedure have
been developed where lipids are simultaneously extracted and
transesterified, reducing reaction time and the amounts of solvent
required, compared to the separate lipid extraction/
 A.G. Capodaglio, A. Callegari / Journal of Environmental Management xxx (2017) 1e7
Table 1
Total solids content and yields of sewage sludges.
Sludge a/b
Total solids a/b
Lipids yield
type (% dry wt) (% dry wt)
Primary 4.2/5.8 25.3/6.81a
Secondary 3.2/4.8 9.3/5.33
Blended 3.1/5.1 21.9/6.42
Stabilized 25.1/- 10.1/-
a
With a reported range of 6e35% depending on wastewater variations.
Data from aOlkiewicz et al.,2012, bZhang et al., 2014a.
transesterification processes. Transesterification reaction times can
also be shortened by higher temperatures and addition of enzymes
(Kargbo, 2010).
Pyrolysis is a promising technique for biodiesel recovery from
urban waste sludge (Leszczynski, 2006; Manara and Zabaniotou,
2012). During the process, sludge is heated (between 300 and
900  C) in an inert atmosphere and decomposed into solid carbo-
naceous residue, oil (condensable volatiles) and permanent gases.
Pyrolysis is considered environmentally friendly, compared to the
widespread application of combustion and incineration, in terms of
clean gas emissions, and applied to sewage sludge has the advan-
tage of concentrating heavy metals (except Hg and Cd) into the final
residue. Usually, considerable amounts of energy are consumed in
the pyrolysis process, hence, careful considerations should be made
when adopting this process.
Menendez et al. (2002) identified a new method for pyrolyzing
sewage sludge using a microwave furnace. Their approach showed
that if raw wet sludge alone is treated in a microwave furnace, only
drying of the sample takes place. However, if the sludge is mixed
with a small amount of a suitable microwave absorber (such as the
char produced in the pyrolysis itself) temperatures of up to 900  C
can be achieved, so that pyrolysis takes place. A similar process was
developed by Xie et al. (2014), using silica compounds as micro-
wave absorbers. Compared with conventional heating, microwaves
save considerable time and energy for an equivalent degree of
drying (or pyrolysis). MAP of sewage sludge makes it possible to
achieve volume reductions greater than 80%, obtaining a porous
carbonaceous residue (char) of basic nature, in addition to gaseous
and liquid fuel products. Capodaglio et al. (2016c) obtained similar
results with sludge alone (without absorbers addition) using a
monomodal microwave synthesizer, rather than a conventional
one. A MMS, unlike a conventional (multimodal) microwave oven,
is capable of matching the impedance between load irradiated and
microwave-generator (magnetron), maximizing the power transfer
to the samples. An advantage of MMS irradiation is that it lowers
the temperature at which efficient pyrolysis occurs. The most effi-
cient conversion rates obtained by Capodaglio et al. (2016c)
occurred at about 280  C, while Menendez et al. (2002) operated
at a maximum temperature of 900  C and Xie et al. (2014) obtained
best yields at 550  C. In addition, the fractioned fuel yield can be
shifted towards the most desirable product type (oil, gas or solid)
for the specific use by appropriately adjusting process parameters.
Table 2 shows biodiesel yields from different waste sludge obtained
by microwave pyrolysis at different temperatures.
Table 2
Process temperature and biodiesel yields for sludge treated with microwave-assisted pyrolysis.
Temp.  C a
280
Oil to total sludge (% dry wt) 12.52
Oil to sludge org. fraction (% dry wt) 25
a
MMS irradiation, no catalyst applied to anaerobically stabilized sludge.
b
Conventional irradiation, with char addition as catalyst, applied to raw sludge.
Data from aCapodaglio et al., 2016c, bXie et al., 2014.
Please cite this article in press as: Capodaglio, A.G., Callegari, A., Feedstock and process influence on biodiesel produced from waste sewage
sludge, Journal of Environmental Management (2017), http://dx.doi.org/10.1016/j.jenvman.2017.03.089
3
Modern engines are very sensitive to fuel quality, therefore
maintaining biodiesel product quality is essential for its continued
Biodiesel yield diffusion, regardless of the generation technology used. In order to
(% dry wt) be classified as diesel, the product must meet ASTM D 6751 specs
13.9 for a series of parameters, such as flash point, closed cup, water and
2.9 sediment, viscosity, sulfated ash, total sulfur, copper strip corrosion,
10.9 cetane number, cloud point, carbon residue, acid number, free and
1.0
total glycerin, phosphorus, and vacuum distillation end point. A
comprehensive review of biodiesel properties and specifications
was recently published by Hoekman et al. (2012). Trans-
esterification is reputed to be the most favourable reaction in
producing biodiesel because it reduces resulting oil viscosity (Daud
et al., 2015). Pyrolysis oils have high carbon and hydrogen contents,
water content is reasonable and flash point is usually high. Pyrol-
ysis oils have good lubricity, but show some corrosiveness. Cetane
index is reduced, which may influence ignition. Viscosity is
increased compared to transesterification-derived oils, which may
influence atomisation quality. Carbon residue and ash content are
both high, indicating potential deposition problems (Yang et al.,
2013). Regardless of the production method used, therefore, bio-
diesel usually undergoes more or less significant post-processing in
order to fulfill marketing requirements, adding to its production
cost.
1.3. Biodiesel and other pyrolysis process by-products
Final products of the pyrolysis process can be classified into the
following fractions: (a) stable (non-condensable) gas (syngas)
mainly consisting of H2, CO, CO2, CH4 and small concentrations of
low molecular weight hydrocarbons, (b) liquids (tar and oil, from
which biodiesel is separated) mainly hydrocarbons, organic acids
and carbonyl compounds of high molecular weight, phenols, aro-
matic compounds, aliphatic alcohols, acetic acid and water and (c)
solid (char), mostly solid carbon and ash (with significant amount
of heavy metals). The process can be adjusted, to a considerable
degree, to produce the most desirable fraction.
All three mentioned groups of products can be considered bio-
fuels. The organic fraction of the pyrolysis liquids (30e40% of the
total liquid), not including the aqueous fraction with hydrosoluble
organic compounds, shows the highest heating value among all the
pyrolysis products, ranging between 22,400 and 28,000 kJ kg
1
(dry basis) (Inguanzo et al., 2002), and is comparable to some
conventional fuels and other waste-residues commonly used as
biofuels. The tar fraction separated by the lighter biodiesel fraction
is an undetermined, complex mixture containing hundreds of
organic compounds belonging to a multitude of chemical groups.
The perceived potential of biodiesel towards a replacement of
liquid fossil fuels in internal combustion engines, and the greater
economic convenience of that extracted from waste sludge
compared to those derived from other feedstocks has focused
research on maximizing pyrolytic production of the liquid fraction.
The syngas products fraction has a heating value comparable to
that of other gases, between 12,000 and 20,000 kJ/m
3, depending
on process conditions. Optimization of sludge pyrolysis could thus
yield gas that would enhance the process energy balance. The
a
400 a/b
450 a/b
500 a/b
550 a/b
600 a
650
11.5 -/8 10.25/11.5 -/20 8.71/18.5 7.31
23 21 17 15
4 A.G. Capodaglio, A. Callegari / Journal of Environmental Management xxx (2017) 1e7
greater diffusion of liquid fuel (diesel) for transportation use at the
moment seems to indicate, in the absence of other developments,
process emphasis on the maximization of the liquid product. As a
general rule, syngas and oil production yields increase (at different
rates) with increasing process temperature, while the solid residue
decreases.
The solid fraction consists of a carbonaceous material known as
char. Its composition is clearly related to that of the other fractions,
and depends on process parameters; ash content and particle size
are, respectively, directly and inversely proportional to pyrolysis
process temperature (Trinh et al., 2013). Char from waste sludge
pyrolysis is pathogen-free and rich in carbon and nutrient contents
(it is often referred to as biochar), has a relatively low heating value,
and high concentrations of ash and heavy metals, that render it
mostly uninteresting for further energetic exploitation. However,
the high contents of other elements N, P, K, Ca, Mg, and S, all
important macronutrients could make the char valuable as a soil
amendmant, especially concerning phosphorus, which is a scarce
element. Sludge char has been shown to contain more than 3% P (by
weight), about 95% of the phosphorus originally contained in the
sludge, therefore pyrolysis could be a promising indirect method to
recycle phosphorus into soil. Studies have demonstrated that bio-
char increased long-term soil nutrient retention, improving fertil-
iser utilisation efficiency and enhancing crop production (Song
et al., 2014). Since heavy metals with high boiling point (e.g., Pb,
Co, Ni, Cu, Zn, and Sr) originally contained in the sludge remain
mostly in the char, in case of its use on farmland, the metal content
must be adequately taken into account. On the other hand, tests
showed that char from sludge pyrolysis is more resistant to metals
lixiviation than raw sludge or incineration ashes, due to the large
quantity of micropores of its structure and the fact that some of the
metal remains bound within the structure of the char mass, rather
than on the surface (Trinh et al., 2013). Short-term studies on
sludge char-enriched soils showed that only Zn and Cu accumu-
lated in plants, compared to reference soils. As, Pb, Ni, Cd and Cr,
that were only enriched 2e4 times compared with reference soils,
showing no obvious accumulation in crops (Song et al., 2014).
Therefore, although char has very little play in the energetic bal-
ance of sludge pyrolysis, it still constitutes a by-product with po-
tential valuable uses that does not necessarily implies additional
disposal costs.
2. Biodiesel characteristics
2.1. Biodiesel characteristics vs. feedstock
The yield and characteristics of biodiesel very widely depending
on feedstock characteristics and production technology. While in
this paper only waste urban sludge is considered as a general
feedstock source, every sludge is different, depending on its initial
source and “production” process. As it can be seen in Table 1,
referred to biodiesel lipid-transesterification processes, among
three sludge types considered (from two generating facilities),
primary sludge generally achieve the greatest lipids and biodiesel
yields. Primary sludge is often a combination of floating grease and
organic solids. Secondary sludge yielded the lowest biodiesel
quantities. Blended sludge, mixture of primary and secondary,
obtained the second best results in one case. The characteristics of
the sludge-producing treatment plant contributing basin, and the
facility operational conditions themselves are likely to cause such
variations in yields. Considering the overall yields of these sludge
types, results apparently show that it would seem more beneficial
to use primary sludge to produce biodiesel. Olkiewicz et al. (2012)
showed that profile comparison between primary, secondary and
blended sludge (from the same source) indicated no substantial
Please cite this article in press as: Capodaglio, A.G., Callegari, A., Feedstock and process influence on biodiesel produced from waste sewage
sludge, Journal of Environmental Management (2017), http://dx.doi.org/10.1016/j.jenvman.2017.03.089
difference in their fatty acids composition. The latter plays an
important role in fuel qualities, determining its resulting viscosity,
oxidation stability, cold flow property, flash point, calorific value
(also called heat content or energy density), etc. Incidentally, those
extracted from sewage sludge usually belong to C10 to C18 groups,
these are excellent for the production of biodiesel. However,
considering that blended sludge is stabilized before disposal, usu-
ally by anaerobic digestion, it should be remembered that signifi-
cant amount of lipids in sludge can affect anaerobic (and aerobic, as
well) processes, inhibiting methanogenesis during digestion
(Carucci et al., 2005). Thus, elimination of lipids from primary
sludge significantly reduces their amount in blended sludge,
potentially improving its methane (biogas) production.
2.2. Biodiesel characteristics vs. production process
In traditional thermal heating with an external heat source,
applied to conventional pyrolysis, heat is transferred from the
surface towards the center of the mass heated by conduction,
convection, and radiation. In addition to being relatively inefficient,
it is also sow and requires long process times. Dielectric heating
(supplied by microwaves) by transforming electromagnetic to
thermal energy, is an energy conversion where microwaves deposit
energy within a material (in-core volumetric heating). Along with
transesterification processes, conventional pyrolysis processes are
relatively well studied and understood, while microwave-assisted
pyrolysis still presents aspects that must be investigated. They are
however recognized, at present, as some of the most promising
methods of enhancing and accelerating thermochemical reactions.
According to literature, there are some possible chemical reaction
enhancements occurring using microwave irradiation techniques,
including thermal effects (influence of rapidly attained high reac-
tion temperatures), specific microwave effects (due to the unique
nature of microwave irradiation mechanism, and non-thermal ef-
fects (chemical transformations acceleration not defined in terms
of other specific effects) (Motasemi and Afzal, 2013) that may
explain some experimental observations, such as those in Table 2.
Zhao et al. (2012) reported the effect of temperature on
microwave-induced pyrolysis of wheat straw biomass, observing
that temperature is an effectual parameter in the microwave py-
rolysis process, causing an increase in the yield of gas products (and
ratio of combustible to total gas from 17.69% to 22.27% weight,
when increased from 400  C to 600  C). Hu et al. (2012) applying
microwave pyrolysis to microalgal biomass showed that bio-oils,
bio-gas and residues yields could be manipulated as needed by
varying applied microwave power levels and catalysts (activated
carbon, CaO, SiC or char) concentration. Application to sewage
sludge allowed Tian et al. (2011) to develop relationships between
mass balance of the products and microwave applied power. They
found, using a sample sludge size of 125 g, that the most efficient
range for transforming sludge into bio-oil was about 400e600 W
(3200e4800 W/kg), while increasing power range to 600e800 W
(4800e6400 W/kg) caused improvement in gas yield, but decrease
in biodiesel yield. These results are not in contrast with findings
observed by Capodaglio et al. (2016c), although such relationships
are not directly universally applicable, but vary from feedstock to
feestock, and with process configuration. As pointed out by
Motasemi and Afzal (2013), yield and quality of pyrolysis value-
added products are affected critical parameters in microwave-
assisted processes, such as type and size of input biomass/mate-
rials, moisture and water content, reaction temperature and time,
microwave output power and type (multimode or monomodal),
reactor design/type, microwave receptors type, size, amount/con-
centration, catalyst type (if any) and concentration, mixing in-
tensity (stirring), type and flow rate of carrier gas.
 A.G. Capodaglio, A. Callegari / Journal of Environmental Management xxx (2017) 1e7
In order to obtain the highest quality and conversion yields,
these variables should be optimized on a case-by-case basis.
Looking at Table 2, referred to pyrolysis technologies, it can be
seen that anaerobically stabilized sludge, pyrolysed at different
temperatures, shows oil yields up to 500  C that are in line with
those of blended and primary sludge in the transesterification
process (greater at lower temperatures), but much higher than that
obtained from the same type of sludge with that process, while raw
sludge (blended) achieves increasing yields with temperature up to
an optimum of 550  C, where the yield is approximately twice that
obtained by transesterification. In these two cases, feedstock
heating modalities between conventional and monomodal irradi-
ation are most probably responsible for the difference in yield of
the two processes, which may be studied and understood only with
very detailed studies, which are complicated by the fact that py-
rolysis processes duration is very short compared to extraction
processes (in the order of minutes). Figs. 1 and 2 show, respectively,
representative chromatograms of pyrolytic oil derived from urban
sludge by different researchers: Fig. 1 shows GC/MS analyses from
the same sludge sample MAP-processed at different temperatures
(Capodaglio et al., 2016c), while Fig. 2 shows results from two
sludge samples by Kwon et al. (2013). It can be seen that process
temperature plays a substantial effect not only on overall biodiesel
yield, but also in its properties.
3. Biodiesel economic considerations
Crude oil prices have been fluctuating between about 40 to
more than 140 US$ per barrel (1 barrel ¼ 31.5 gallons) in the last
decade alone. As of 2010, the estimated cost of industrial produc-
tion of biodiesel from dry sludge was $ 3.11 per gallon (1
gal ¼ 3.875 L) of biodiesel, compared to $3.00 per gallon for fossil
diesel (with crude sold at 78 US$/barrel). The biodiesel price was
then broken down to $2.06/gal for preprocessing, extraction and
stabilization, and $1.05/gal for other miscellaneous process costs
(Kargbo, 2010). To be competitive, this needs to be reduced
(without considering temporary incentives) to levels at or below
petroleum diesel costs: this objective may not be so far away. A
study from the US Dept. of Energy (DOE; Haq, 2012) estimated the
economic data pertaining to biodiesel production from agricultural
biomasses pyrolysis shown below (Table 3).
The figures show that the most dramatic economic progress in
Fig. 1. Chromatograms of pyrolytic oil from MAP at different temperatures, ranging from 270 to 600  C (From Capodaglio et al., 2016a,b,c).
Please cite this article in press as: Capodaglio, A.G., Callegari, A., Feedstock and process influence on biodiesel produced from waste sewage
sludge, Journal of Environmental Management (2017), http://dx.doi.org/10.1016/j.jenvman.2017.03.089
5
biodiesel industry development is expected in fuel post-processing
(that is, upgrading extracted products to stable, standard-
complying fuels) with a cost reduction expected to reach 90%
from 2009, and to a smaller degree (
43%) in feedstock prices.
Therefore, from the data shown and hypothesizing exclusive use
of urban waste sludge as feedstock, which could be procured at the
mere cost of transportation (or even with an additional income
linked to a gate fee - it is, after all, a waste to be disposed of), thus
assuming no feedstock costs, under the envisioned technological
progress the cost a gallon of pyrolytic sludge-derived biodiesel
should stabilize at around, or below, 1.5 $. This suggests that bio-
diesel production from sludge could be very profitable in the long
run, especially considering that fossil oil is expected to increase in
price in the long run.
Studies have estimated that, using all annually available
wastewater treatment plant sludge generated in the USA for con-
version to oil, 3.6  109 gallons (14  106 m3) of biodiesel could be
produced, or about 1% of total US annual consumption (Dufreche
et al., 2007). Considering that the expected 2020 EU sludge pro-
duction is approximately double that of the USA, and using the
same conversion factors, it can be estimated that about 26  106 m3
of biodiesel could be produced in Europe annually (or about 15% of
the overall traffic-related diesel demand, as of 2012). Additional
revenue from other pyrolysis-generated fractions is not discussed
in the cited studies.
4. Future directions in sewage sludge biodiesel production
Considerable attention has been given recently to renewable
substitutes for fossil fuels, due to the concurrent problems of fossil
fuel depletion, environmental degradation due to population in-
crease and waste amounts generation, and GHG emissions, linked
to global climate change. Governments and regulatory agencies
worldwide are thus promoting the substitution of fossil fuels with
biofuels from various originating biomasses. Acceptance of the
Kyoto protocol will lead to more global biodiesel production: it is
anticipated that Kyoto-related policies will lead to a total bio-fuel
demand in EU of around 30.3 million tons in 2020. With global
human population increase, more land will be needed to produce
food, thus food/energy competition could increase production costs
of biodiesel plants, both edible and not. Such problem has already
emerged in Asia, where vegetable oil prices are relatively high. This
6 A.G. Capodaglio, A. Callegari / Journal of Environmental Management xxx (2017) 1e7

Fig. 2. Chromatograms of pyrolytic oil from MAP from two sludge samples from different sources at equal MAP conditions (From Kwon et al., 2013).

Table 3 conditions and outputs have been obtained in some cases (Tian
Projected costs (in US$/gallon) of renewable diesel via pyrolysis of agricultural et al., 2011) but are applicable only in those specific experimental
feedstocks.
conditions.
Items 2009 2012 2012e2017 Annual 2017 There are however still a few limitations which affect MAP
cost decrease industrialization: absence of sufficient data and methods to directly
Feedstock 1.33 0.99 (
25.6%)
5% 0.75 quantify the dielectric properties of input feedstocks, uncertainty
Preparation/extraction 0.54 0.52
4% 0.34 about the design and development of full-scale microwave-assisted
Stabilization 4.69 2.01 (
57%)
34% 0.47 conversion unit, raising uncertainty about the actual cost of the
Finishing 0.30 0.29
4% 0.11
Margin 0.82 0.74
2% 0.65
process, and issues about the chemical reactivity nature of the
Total $/gallon 7.68 4.55 2.32 microwave heating methods.
To boost biodiesel production in transesterification processes
Elaborated from Haq, 2012.
separate utilization of different sludge fractions, treating them for
maximum lipids extraction was suggested (Dufreche et al., 2007).
is a potential challenge to biodiesel production. Therefore, the use This may not have the same effect when using pyrolysis or MAP;
of non-edible oil, genetically engineered plants, microalgae or however, another possibility to enhance feedstock would be for
waste-derived feedstocks can be proper solutions to ensure the wastewater operators to utilize microorganisms selected for their
sustainability of biodiesel production in the future (Atabani et al., higher oil-producing capabilities (Kargbo, 2010). Oleaginous mi-
2012). croorganisms as lipid source have shown great advantage, due to
Wastewater sludge has shown to be a compatible feedstock for their faster growth rate and higher lipid contents (up to 80% d.w.)
biodiesel production, yielding high energy gains, all the while compared to oilseed crops (Zhang et al., 2013). Researchers have
minimizing the problem of sludge disposal itself, which is energy identified consortia of high oil-producing yeast, bacteria and fungi
consuming and resource wasting. Evaluation of GHG emissions of that, in wastewater supplemented with sugar, boosted oil yields
biodiesel production from sludge indicates that this constitutes is a (Marjakangas, 2015). Compared to other microorganisms, many
carbon dioxide capture or recovery method, with great impact on gene regulation mechanisms in fatty acid synthesis by bacteria are
emissions. All considered, this seem therefore to constitute a quite already understood. Therefore, it could be relatively easy to use
environmentally friendly solution. biological engineering technology, genetic engineering, and meta-
Thermochemical and biochemical processes can be applied to bolic engineering to modify bacteria to improve their oil accumu-
upgrade this biomass to fuel. Pyrolysis, a thermochemical method lation. It was reported that a metabolically engineered Escherichia
of energy recovery, offers higher energy production efficiency and coli could produce biodiesel directly, and that fatty acid esters
the generation of a variety of different products. MAP, an evolution concentrations of 0.7 g/l to 3.8 g/l were achieved by fed-batch
of the original pyrolysis process, offers some unique advantages fermentation using renewable carbon sources (Thevenieau and
compared to the former, like shorter processing time and energy Nicaud, 2013). Undoubtedly, the implementation of such technol-
savings. In this method, feedstock properties (raw vs. stabilized ogy would imply a profound re-thinking of wastewater treatment
sludge, lipid content, sludge originating process train) and reaction processes design and operation, to achieve residual biomass opti-
conditions are two effectual elements influencing characterization mization, but would potentially increase fewfolds biodiesel pro-
and yield of final products. Somewhat contrasting results have been duction from waste sludges.
obtained by different researchers concerning optimal yield tem- The presence of pharmaceutical chemicals in sludge poses
peratures and specific product fractions yield, although the pro- somewhat of a challenge, that can be overcome by careful selection
cesses used cannot be directly compared with each other of sludge conversion technologies: in all likelihood, pyrolysis and
(Capodaglio et al., 2016c; Xie et al., 2014; Kwon et al., 2013). The MAP processes will be able to destroy and mineralize such re-
MAP process used by Capodaglio et al. (2016c) uses a special siduals, while extraction with transesterification may actually
monomodal wave emission source, and appears to offer better ef- concentrate them.
ficiency than processes using multi-modal ones. Functional re- In conclusion, pyrolysis is one of the most important biocon-
lationships between mass balance of the products, process version processes that have been tested to date for waste sewage

Please cite this article in press as: Capodaglio, A.G., Callegari, A., Feedstock and process influence on biodiesel produced from waste sewage
sludge, Journal of Environmental Management (2017), http://dx.doi.org/10.1016/j.jenvman.2017.03.089
 A.G. Capodaglio, A. Callegari / Journal of Environmental Management xxx (2017) 1e7
sludge conversion to biodiesel, and researches are trying to develop
more economic and efficient microwave-assisted pyrolysis unit
that can maximize the extraction of the most desirable products.
5. Conclusions
Biofuels derived from renewable bio-mass resources provide a
strategic advantage to promote sustainable development and
supplement conventional energy sources. Routes to convert
biomass virgin resources, biomass residues and wastes (non-con-
ventional sources), including municipal solid wastes and sewage
sludge into value-added products are being intensively investi-
gated. Waste sewage sludge, in need of safe disposal, and available
in large quantities and extremely low cost has shown high potential
as a feedstock, with yields comparable to those of commonly used
crops, and low costs. Pyrolysis, and in particular MAP has shown
high efficiency of biodiesel extraction from waste sludges, but still
need to be optimized in order to be successfully applied at an in-
dustrial scale. Pyrolysis can provide a variety of energy-dense
products in different phases: solid carbonaceous residue (char/
biochar), liquid (biodiesel), and gas (syngas). All of them are po-
tential substitutes for currently available fossil fuels, however,
biodiesel is more desired given it larger flexibility of use in the
existing application framework.
Adoption of renewable fuels has many advantages, such as
natural energy resource security improvement, emission and
pollution reduction, and it can be a suitable pathway for a more
sustainable development. The creation of dependable bioenergy-
from-wastes production chain, industry acceptance, cost reduc-
tion, and maturity of processing technology are paramount factors
to establish a sustainable biofuel market in the long-term.
References
Atabani, A.E., Silitonga, A.S., Badruddin, I.A., Mahlia, T.M.I., Masjuki, H.H.,
Mekhilef, S., 2012. A comprehensive review on biodiesel as an alternative en-
ergy resource and its characteristics. Renew. Sustain Energy Rev. 16,
2070e2093.
Basha, S.A., Gopal, K.R., Jebaraj, S., 2009. A review on biodiesel production, com-
bustion, emissions and performance. Renew. Sust. Energy Rev. 13, 1628e1634.
Bhatti, H.N., Hanif, M.A., Qasim, M., Ata-ur-Rehman, 2008. Biodiesel production
from waste tallow. Fuel 87, 2961e2966.
Capodaglio, A.G., Callegari, A., Lopez, M.V., 2016a. European framework for the
diffusion of biogas uses: emerging technologies, acceptance, incentive strate-
gies, and institutional-regulatory support. Sustainability 8 (4), 298.
Capodaglio, A.G., Ranieri, E., Torretta, V., 2016b. Process enhancement for maxi-
mization of methane production in codigestion biogas plants. Manag. Environ.
Qual. 27 (3), 289e298.
Capodaglio, A.G., Callegari, A., Dondi, D., 2016c. Microwave-induced pyrolysis for
production of sustainable biodiesel from waste sludges. Waste Biomass Valor. 7
(4), 703e709.
Carucci, G., Carrasco, F., Trifoni, K., Majone, M., Beccari, M., 2005. Anaerobic
digestion of food industry wastes: effect of codigestion on methane yield. J. Env.
Eng. 131, 1037e1045.
Daud, N.M., Abdullah, S.R.S., Abu Hasan, H., Yaakob, Z., 2015. Production of biodiesel
and its wastewater treatment technologies: a review. Process Saf. Environ. Prot.
94, 487e508.
David, B., et al., 2008. Environmental, Economic and Social Impacts of the Use of
Sewage Sludge on Land Draft Summary Report 2 Baseline Scenario, Analysis of
Risk and Opportunities, for the European Commission. DG Environment under
Study Contract DG ENV.G.4/ETU/2008/0076r.
Dufreche, S., Hernandez, R., French, T., Sparks, D., Zappi, M., Alley, E., 2007.
Extraction of lipids from municipal wastewater plant microorganisms for pro-
duction of biodiesel. J. Am. Oil Chem. Soc. 84, 181e187.
EDB, 2015. European Biodiesel Board. http://www.ebb-eu.org/stats.php (Accessed
Dec 2015).
Haq, Z., 2012. Advanced Biofuels Cost of Production. Aviation Biofuels Conference
Department of Energy Biomass Program. Office of the Biomass Program. http://
Please cite this article in press as: Capodaglio, A.G., Callegari, A., Feedstock and process influence on biodiesel produced from waste sewage
sludge, Journal of Environmental Management (2017), http://dx.doi.org/10.1016/j.jenvman.2017.03.089
7
eere.energy.gov.
Hoekman, S.K., Broch, A., Robbins, C., Ceniceros, E., Natarajan, E., 2012. Review of
biodiesel composition, properties, and specifications. Renew. Sustain. Energy
Rev. 16, 143e169.
Hossain, A.B.M.S., Mekhled, M.A., 2010. Biodiesel fuel production from waste canola
cooking oil as sustainable energy and environmental recycling process. AJCS 4,
543e549.
Hu, Z., Ma, X., Chen, C., 2012. A study on experimental characteristic of microwave-
assisted pyrolysis of microalgae. BioresourceTechnology 107, 487e493.
Inguanzo, M., Domínguez, A., Mene ndez, J.A., Blanco, C.G., Pis, J.J., 2002. On the
pyrolysis of sewage sludge: the influence of pyrolysis conditions on solid, liquid
and gas fractions. J. Anal. Appl. Pyrol. 63, 209e222.
Kargbo, D.M., 2010. Biodiesel production from municipal sewage sludges. Energy
Fuels 24, 2791e2794.
Kwon, E.E., Kim, S., Jeon, Y.J., Yi, H., 2012. Biodiesel production from sewage sludge:
new paradigm for mining energy from municipal hazardous material. Environ.
Sci. Technol. 46, 10222e10228.
Kwon, E.E., Yi, H., Kwon, H.H., 2013. Urban energy mining from sewage sludge.
Chemosphere 90, 1508e1513.
Leszczynski, S., 2006. Pyrolysis of sewage sludge and municipal organic waste. Acta
Metall. Slovaca 12, 257e261.
Manara, P., Zabaniotou, A., 2012. Towards sewage sludge based biofuels via ther-
mochemical conversion e a review. Renew. Sustain. Energy Rev. 16, 2566e2582.
Marjakangas, J., 2015. PhD Thesis. Production of Oleaginous Microbial Biomass by
Reusing Wastewaters, vol. 1348. Tampere University of Technology. Publication
(Tampere University of Technology).
Menendez, J.A., Inguanzo, M., Pis, J.J., 2002. Microwave-induced pyrolysis of sewage
sludge. Water Res. 36 (13), 3261e3264.
Motasemi, F., Afzal, M.T., 2013. A review on the microwave-assisted pyrolysis
technique. Renew. Sustain. Energy Rev. 28, 317e330.
Olkiewicz, M., Fortuny, A., Stüber, F., Fabregat, F., Font, J., Bengoa, C., 2012. Evalua-
tion of different sludges from WWTP as a potential source for biodiesel pro-
duction. Proced. Eng. 42, 634e643.
Pastore, C., Lopez, A., Lotito, V., Mascolo, G., 2013. Biodiesel from dewatered
wastewater sludge: a two-step process for a more advantageous production.
Chemosphere 92, 667e673.
Raboni, M., Viotti, P., Capodaglio, A.G., 2015. A comprehensive analysis of the cur-
rent and future role of biofuels for transport in the European union (EU). Revista
Ambiente Agua 9 (10).
Siddiquee, M.N., Rohani, S., 2011. Lipid extraction and biodiesel production from
municipal sewage sludges: a review. Ren. Sust. Energy Rev. 15 (2), 1067e1072.
Song, X.D., Xue, X.Y., Chen, D.Z., He, P.J., Dai, X.h., 2014. Application of biochar from
sewage sludge to plant cultivation: influence of pyrolysis temperature and
biochar-to-soil ratio on yield and heavy metal accumulation. Chemosphere 109,
213e220.
Thevenieau, F., Nicaud, J.M., 2013. Microorganisms as sources of oils. OCL 20 (6),
D603.
Tian, Y., Zuo, W., Ren, Z., Chen, D., 2011. Estimation of a novel method to produce
bio-oil from sewage sludge by microwave pyrolysis with the consideration of
efficiency and safety. Bioresour. Technol. 102, 2053e2061.
Trinh, T.N., Jensen, P.A., Dam-Johansen, K., Knudsen, N.O., Sørensen, H.R., 2013. In-
fluence of the pyrolysis temperature on sewage sludge product distribution,
bio-oil, and char properties. Energy Fuels 27, 1419e1427.
Van Gerpen, J., 2004. Business Management for Biodiesel Producers. National
Renewable Energy Lab, Golden, CO.
Wallace, T., Gibbons, A., O'Dwyer, M., Curran, T.P., 2016. International evolution of
fat, oil and grease (FOG) waste management. A review. J. Environ. Manag. 187,
424e435.
Xie, Q., Peng, P., Liu, S., Min, M., Cheng, Y., Wan, Y., Li, Y., Lin, X., Liu, Y., Chen, P.,
Ruan, R., 2014. Fast microwave-assisted catalytic pyrolysis of sewage sludge for
bio-oil production. Bioresour. Technol. 172, 162e168.
Yang, Y., Brammer, J.G., Ouadi, M., Samanya, Y., Hornung, A., Xu, H.M., Li, Y., 2013.
Characterisation of waste derived intermediate pyrolysis oils for use as diesel
engine fuels. Fuel 103, 247e257.
Zhang, X., Yan, S., Tyagi, R.D., Surampalli, R.Y., 2013. Energy balance and greenhouse
gas emissions of biodiesel production from oil derived from wastewater and
wastewater sludge. Renew. Energy 55, 392e403.
Zhang, X., Yan, S., Tyagi, R.D., Surampalli, R.Y., Vale ro, J.R., 2014a. Wastewater sludge
as raw material for microbial oils production. Appl. Energy 135, 192e201.
Zhang, L., Xu, C., Champagne, P., Mabee, W., 2014b. Overview of current biological
and thermo-chemical treatment technologies for sustainable sludge manage-
ment. Waste Manag. Res. 32, 586.
Zhao, X., Wang, M., Liu, H., Li, L., Ma, C., Song, Z., 2012. A microwave reactor for
characterization of pyrolyzed biomass. BioresourceTechnology 104, 673e678.
Zhu, F., Zhao, L., Jiang, H., Zhang, Z., Xiong, Y., Qi, J., Wang, J., 2014. Comparison of the
lipid content and biodiesel production from municipal sludge using three
extraction methods. Energy Fuels 28, 5277e5283.