Sie sind auf Seite 1von 7

Journal of Environmental Management xxx (2017) 1e7

Contents lists available at ScienceDirect

Journal of Environmental Management


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

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.


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

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 uncompetitive with the food market, and readily available.
produced from lignocellulosic and waste materials and could Currently, biodiesel diffusion is limited mostly by high raw
enable far greater reductions in greenhouse gases (GHG) emission material costs. Since waste sludge, generally, can be considered cost
(Capodaglio et al., 2016a). In 2009, biodiesel represented about 75% free (or even associated with a “gate fee” for its processing) and
of total biofuels produced in the EU. If produced to comply with could be made by up to 30% (by weight) lipid fraction (Dufreche
ASTM D6751 (the international standard of biofuels), it can be used et al., 2007), which could then be processed into FAMEs, it could
for transportation and industrial purposes, and represents a valid form an unexploited and almost endless source of cheap and
alternative to conventional diesel because is renewable, biode- readily available feedstock for biodiesel production.
gradable, less toxic, and has low emission profiles. With a similar Sewage Sludge contains a variety of organic and inorganic
energy density to diesel, it can be used directly without any vehicle compounds originally contained in wastewater. The composition of
or engine modification, and does not require a new type of refu- sludge collected in primary sedimentation basins (primary sludge)
eling infrastructure. For these reasons, the production of biodiesel consists to a high degree of undegraded organic matters. Secondary
in the EU has increased from 3.6 billion liters in 2005 to 10.7 billion sludge, resulting from the interaction of microorganisms with
liters in 2010 (EDB, 2015; Thevenieau and Nicaud, 2013), initially organic matter in a process called activated sludge, exists normally
from feedstocks such as soybean, canola, rapeseed, sunflower, in form of flocs, which besides living and dead biomass contain
palm, and coconut oils. Still, biodiesel production is currently organic and mineral parts. Organic materials present in the waste
limited due to high raw material costs, lack of agricultural lands and water are detergents, pesticides, fats, oil and grease, colorings,
perceived conflict and impact on food prices. The search for cheaper solvents, phenols etc. Digested sludge is a mixture of primary and
feedstocks has turned towards various forms of waste, alternative secondary sludge treated in an anoxic reactor to stabilize (reduce)
raw materials, including waste animal fats, cooking oils (Bhatti its organic content, often with recovery of “biogas” (a mix of
et al., 2008; Hossain and Mekhled, 2010; Wallace et al., 2016) and methane and CO2 gases with other impurities). Less frequently,
lipids in sewage sludge (Dufreche et al., 2007; Zhang et al., 2014a). sludge can be stabilized aerobically, although this process is quite
Kwon et al. (2012) showed that sewage sludge could produce sig- expensive and energetically disadvantageous. It has been claimed
nificant amounts of lipids at low cost, with high yields of fatty acids that the yield of FAMEs from primary sludge is greater than that of
methyl esters (FAMEs), which are the main ingredients of the fuel. activated sludge. Lipid extraction from raw sludge would require
Traditionally, sewage sludge has been processed for decades in large amounts of organic solvents in stirred and heated vessels.
anaerobic tanks to produce biogas, a mixture of CH4 and CO2 that Dewatered sludge (solids content 10e20%) is denser and hinders
can be used as such or further refined to obtain bio-methane, a lipid extraction, however, lipid extraction from dried sludge (solids
renewable fuel with characteristics practically identical to those of content above 35%) is feasible, after adequate pretreatment
fossil methane (Zhang et al., 2014b; Capodaglio et al., 2016b). (centrifugation and/or filtration processes) to obtain the proper
However, recent work has demonstrated that the production of humidity content.
biodiesel using the lipids extracted from sewage sludge could be Average characteristics and yields of different sludge types re-
economically feasible because of the remarkably high yield of oil ported in literature are shown in Table 1. The wide lipid yields for
and low cost of this feedstock (wastewater sludge can be consid- primary sludges will depend on plant configuration, i.e. on mixing
ered “free”, except for transportation costs), as compared to con- of recovered floating oil and grease with the primary sludge. Such
ventional biodiesel feedstocks (Siddiquee and Rohani, 2011). configuration choices would have a significant effect on lipid yield.
The purpose of the study, having already demonstrated the
possibility of recovering biodiesel from waste sludge materials by 1.2. Technologies for biodiesel production from waste sludges
microwave-assisted pyrolysis (MAP) process (Xie et al., 2014;
Capodaglio et al., 2016c), is to attempt a more encompassing Two main technologies are nowadays used for biodiesel pro-
analysis of the process itself, in order to define its outcome limits duction from wastewater sludge: lipid transesterification and py-
and overall sustainability. In a previous experimental study rolysis. Several other technological processes have been studied
(Capodaglio et al., 2016c), the authors concentrated on the sludge and applied for biodiesel production from sludge and other feed-
oil production potential by MAP, showing that under specific cir- stocks. Biodiesel consists of FAMEs, when methanol is the alcohol
cumstances the process itself can be energetically positive, but used in the transesterification process of lipids, or fatty acid alkyl
contributions of generated syngas and char were totally neglected. esters (FAAEs) when produced via base-and/or-acid-catalyzed
These products can bring additional value to the process. Re- transesterification. In a typical process, triglycerides with low free
lationships between feedstock properties, process characteristics fatty acid (FFA) (less than 0.5%) content are transesterified with
and products yields are further assessed in this work. methanol (MeOH) in the presence of alkaline homogeneous cata-
lyst such as potassium hydroxide (Kwon et al., 2013).
1.1. Waste urban sludge as a biodiesel feedstock Alternative approaches for dealing directly with dewatered
sludge while minimizing the energy requirement of the entire
Feedstock selection is one of the most important aspects that process have been investigated: (i) direct methanolysis and (ii)
should be taken into account, determining the economics of the preliminary extraction with hexane of the lipidic fraction and
entire biodiesel (and other resources) recovery process. As a gen- subsequent methanolysis into FAMEs (Pastore et al., 2013). Bio-
eral rule, in every production line, feedstock price should not be diesel yields from lipids extracted by different methods, i.e. acid
more than 50% of the production cost. Until recently, it was esti- hydrolysis, Soxhlet method, and water bath shaking method differ
mated that oils used as feedstock claimed about 80% of production considerably: in a study by Zhu et al. (2014) they were 1.33, 6.73,
costs: for this reason, many researchers believe that waste sludge and 4.92% (dry weight), with purity values, determined by GCMS,
has ideal characteristics for a basic biodiesel feedstock (Van Gerpen, of 97.5, 94.3, and 83.3%, respectively. Optimum production of bio-
2004). Unlike other common feedstocks used for biodiesel pro- diesel is faced with considerable challenges as lipids are extracted
duction (food and non-food crops) which prices may experience and then transesterified. In situ transesterification procedure have
severe fluctuations due to market conditions and competition with been developed where lipids are simultaneously extracted and
other uses, sludge is a waste product, abundantly produced in large transesterified, reducing reaction time and the amounts of solvent
quantities at an almost constant rate during the year, required, compared to the separate lipid extraction/

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 3

Table 1 Modern engines are very sensitive to fuel quality, therefore


Total solids content and yields of sewage sludges. maintaining biodiesel product quality is essential for its continued
Sludge a/b
Total solids a/b
Lipids yield Biodiesel yield diffusion, regardless of the generation technology used. In order to
type (% dry wt) (% dry wt) (% dry wt) be classified as diesel, the product must meet ASTM D 6751 specs
Primary 4.2/5.8 25.3/6.81a 13.9 for a series of parameters, such as flash point, closed cup, water and
Secondary 3.2/4.8 9.3/5.33 2.9 sediment, viscosity, sulfated ash, total sulfur, copper strip corrosion,
Blended 3.1/5.1 21.9/6.42 10.9 cetane number, cloud point, carbon residue, acid number, free and
Stabilized 25.1/- 10.1/- 1.0
total glycerin, phosphorus, and vacuum distillation end point. A
a
With a reported range of 6e35% depending on wastewater variations. comprehensive review of biodiesel properties and specifications
Data from aOlkiewicz et al.,2012, bZhang et al., 2014a.
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
transesterification processes. Transesterification reaction times can
et al., 2015). Pyrolysis oils have high carbon and hydrogen contents,
also be shortened by higher temperatures and addition of enzymes
water content is reasonable and flash point is usually high. Pyrol-
(Kargbo, 2010).
ysis oils have good lubricity, but show some corrosiveness. Cetane
Pyrolysis is a promising technique for biodiesel recovery from
index is reduced, which may influence ignition. Viscosity is
urban waste sludge (Leszczynski, 2006; Manara and Zabaniotou,
increased compared to transesterification-derived oils, which may
2012). During the process, sludge is heated (between 300 and
influence atomisation quality. Carbon residue and ash content are
900  C) in an inert atmosphere and decomposed into solid carbo-
both high, indicating potential deposition problems (Yang et al.,
naceous residue, oil (condensable volatiles) and permanent gases.
2013). Regardless of the production method used, therefore, bio-
Pyrolysis is considered environmentally friendly, compared to the
diesel usually undergoes more or less significant post-processing in
widespread application of combustion and incineration, in terms of
order to fulfill marketing requirements, adding to its production
clean gas emissions, and applied to sewage sludge has the advan-
cost.
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 1.3. Biodiesel and other pyrolysis process by-products
when adopting this process.
Menendez et al. (2002) identified a new method for pyrolyzing Final products of the pyrolysis process can be classified into the
sewage sludge using a microwave furnace. Their approach showed
following fractions: (a) stable (non-condensable) gas (syngas)
that if raw wet sludge alone is treated in a microwave furnace, only mainly consisting of H2, CO, CO2, CH4 and small concentrations of
drying of the sample takes place. However, if the sludge is mixed
low molecular weight hydrocarbons, (b) liquids (tar and oil, from
with a small amount of a suitable microwave absorber (such as the which biodiesel is separated) mainly hydrocarbons, organic acids
char produced in the pyrolysis itself) temperatures of up to 900  C
and carbonyl compounds of high molecular weight, phenols, aro-
can be achieved, so that pyrolysis takes place. A similar process was matic compounds, aliphatic alcohols, acetic acid and water and (c)
developed by Xie et al. (2014), using silica compounds as micro-
solid (char), mostly solid carbon and ash (with significant amount
wave absorbers. Compared with conventional heating, microwaves of heavy metals). The process can be adjusted, to a considerable
save considerable time and energy for an equivalent degree of
degree, to produce the most desirable fraction.
drying (or pyrolysis). MAP of sewage sludge makes it possible to All three mentioned groups of products can be considered bio-
achieve volume reductions greater than 80%, obtaining a porous
fuels. The organic fraction of the pyrolysis liquids (30e40% of the
carbonaceous residue (char) of basic nature, in addition to gaseous total liquid), not including the aqueous fraction with hydrosoluble
and liquid fuel products. Capodaglio et al. (2016c) obtained similar
organic compounds, shows the highest heating value among all the
results with sludge alone (without absorbers addition) using a pyrolysis products, ranging between 22,400 and 28,000 kJ kg1
monomodal microwave synthesizer, rather than a conventional
(dry basis) (Inguanzo et al., 2002), and is comparable to some
one. A MMS, unlike a conventional (multimodal) microwave oven, conventional fuels and other waste-residues commonly used as
is capable of matching the impedance between load irradiated and biofuels. The tar fraction separated by the lighter biodiesel fraction
microwave-generator (magnetron), maximizing the power transfer is an undetermined, complex mixture containing hundreds of
to the samples. An advantage of MMS irradiation is that it lowers organic compounds belonging to a multitude of chemical groups.
the temperature at which efficient pyrolysis occurs. The most effi- The perceived potential of biodiesel towards a replacement of
cient conversion rates obtained by Capodaglio et al. (2016c) liquid fossil fuels in internal combustion engines, and the greater
occurred at about 280  C, while Menendez et al. (2002) operated economic convenience of that extracted from waste sludge
at a maximum temperature of 900  C and Xie et al. (2014) obtained compared to those derived from other feedstocks has focused
best yields at 550  C. In addition, the fractioned fuel yield can be
research on maximizing pyrolytic production of the liquid fraction.
shifted towards the most desirable product type (oil, gas or solid) The syngas products fraction has a heating value comparable to
for the specific use by appropriately adjusting process parameters.
that of other gases, between 12,000 and 20,000 kJ/m3, depending
Table 2 shows biodiesel yields from different waste sludge obtained on process conditions. Optimization of sludge pyrolysis could thus
by microwave pyrolysis at different temperatures.
yield gas that would enhance the process energy balance. The

Table 2
Process temperature and biodiesel yields for sludge treated with microwave-assisted pyrolysis.

Temp.  C a
280 a
400 a/b
450 a/b
500 a/b
550 a/b
600 a
650

Oil to total sludge (% dry wt) 12.52 11.5 -/8 10.25/11.5 -/20 8.71/18.5 7.31
Oil to sludge org. fraction (% dry wt) 25 23 21 17 15
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
4 A.G. Capodaglio, A. Callegari / Journal of Environmental Management xxx (2017) 1e7

greater diffusion of liquid fuel (diesel) for transportation use at the difference in their fatty acids composition. The latter plays an
moment seems to indicate, in the absence of other developments, important role in fuel qualities, determining its resulting viscosity,
process emphasis on the maximization of the liquid product. As a oxidation stability, cold flow property, flash point, calorific value
general rule, syngas and oil production yields increase (at different (also called heat content or energy density), etc. Incidentally, those
rates) with increasing process temperature, while the solid residue extracted from sewage sludge usually belong to C10 to C18 groups,
decreases. these are excellent for the production of biodiesel. However,
The solid fraction consists of a carbonaceous material known as considering that blended sludge is stabilized before disposal, usu-
char. Its composition is clearly related to that of the other fractions, ally by anaerobic digestion, it should be remembered that signifi-
and depends on process parameters; ash content and particle size cant amount of lipids in sludge can affect anaerobic (and aerobic, as
are, respectively, directly and inversely proportional to pyrolysis well) processes, inhibiting methanogenesis during digestion
process temperature (Trinh et al., 2013). Char from waste sludge (Carucci et al., 2005). Thus, elimination of lipids from primary
pyrolysis is pathogen-free and rich in carbon and nutrient contents sludge significantly reduces their amount in blended sludge,
(it is often referred to as biochar), has a relatively low heating value, potentially improving its methane (biogas) production.
and high concentrations of ash and heavy metals, that render it
mostly uninteresting for further energetic exploitation. However, 2.2. Biodiesel characteristics vs. production process
the high contents of other elements N, P, K, Ca, Mg, and S, all
important macronutrients could make the char valuable as a soil In traditional thermal heating with an external heat source,
amendmant, especially concerning phosphorus, which is a scarce applied to conventional pyrolysis, heat is transferred from the
element. Sludge char has been shown to contain more than 3% P (by surface towards the center of the mass heated by conduction,
weight), about 95% of the phosphorus originally contained in the convection, and radiation. In addition to being relatively inefficient,
sludge, therefore pyrolysis could be a promising indirect method to it is also sow and requires long process times. Dielectric heating
recycle phosphorus into soil. Studies have demonstrated that bio- (supplied by microwaves) by transforming electromagnetic to
char increased long-term soil nutrient retention, improving fertil- thermal energy, is an energy conversion where microwaves deposit
iser utilisation efficiency and enhancing crop production (Song energy within a material (in-core volumetric heating). Along with
et al., 2014). Since heavy metals with high boiling point (e.g., Pb, transesterification processes, conventional pyrolysis processes are
Co, Ni, Cu, Zn, and Sr) originally contained in the sludge remain relatively well studied and understood, while microwave-assisted
mostly in the char, in case of its use on farmland, the metal content pyrolysis still presents aspects that must be investigated. They are
must be adequately taken into account. On the other hand, tests however recognized, at present, as some of the most promising
showed that char from sludge pyrolysis is more resistant to metals methods of enhancing and accelerating thermochemical reactions.
lixiviation than raw sludge or incineration ashes, due to the large According to literature, there are some possible chemical reaction
quantity of micropores of its structure and the fact that some of the enhancements occurring using microwave irradiation techniques,
metal remains bound within the structure of the char mass, rather including thermal effects (influence of rapidly attained high reac-
than on the surface (Trinh et al., 2013). Short-term studies on tion temperatures), specific microwave effects (due to the unique
sludge char-enriched soils showed that only Zn and Cu accumu- nature of microwave irradiation mechanism, and non-thermal ef-
lated in plants, compared to reference soils. As, Pb, Ni, Cd and Cr, fects (chemical transformations acceleration not defined in terms
that were only enriched 2e4 times compared with reference soils, of other specific effects) (Motasemi and Afzal, 2013) that may
showing no obvious accumulation in crops (Song et al., 2014). explain some experimental observations, such as those in Table 2.
Therefore, although char has very little play in the energetic bal- Zhao et al. (2012) reported the effect of temperature on
ance of sludge pyrolysis, it still constitutes a by-product with po- microwave-induced pyrolysis of wheat straw biomass, observing
tential valuable uses that does not necessarily implies additional that temperature is an effectual parameter in the microwave py-
disposal costs. 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,
2. Biodiesel characteristics when increased from 400  C to 600  C). Hu et al. (2012) applying
microwave pyrolysis to microalgal biomass showed that bio-oils,
2.1. Biodiesel characteristics vs. feedstock bio-gas and residues yields could be manipulated as needed by
varying applied microwave power levels and catalysts (activated
The yield and characteristics of biodiesel very widely depending carbon, CaO, SiC or char) concentration. Application to sewage
on feedstock characteristics and production technology. While in sludge allowed Tian et al. (2011) to develop relationships between
this paper only waste urban sludge is considered as a general mass balance of the products and microwave applied power. They
feedstock source, every sludge is different, depending on its initial found, using a sample sludge size of 125 g, that the most efficient
source and “production” process. As it can be seen in Table 1, range for transforming sludge into bio-oil was about 400e600 W
referred to biodiesel lipid-transesterification processes, among (3200e4800 W/kg), while increasing power range to 600e800 W
three sludge types considered (from two generating facilities), (4800e6400 W/kg) caused improvement in gas yield, but decrease
primary sludge generally achieve the greatest lipids and biodiesel in biodiesel yield. These results are not in contrast with findings
yields. Primary sludge is often a combination of floating grease and observed by Capodaglio et al. (2016c), although such relationships
organic solids. Secondary sludge yielded the lowest biodiesel are not directly universally applicable, but vary from feedstock to
quantities. Blended sludge, mixture of primary and secondary, feestock, and with process configuration. As pointed out by
obtained the second best results in one case. The characteristics of Motasemi and Afzal (2013), yield and quality of pyrolysis value-
the sludge-producing treatment plant contributing basin, and the added products are affected critical parameters in microwave-
facility operational conditions themselves are likely to cause such assisted processes, such as type and size of input biomass/mate-
variations in yields. Considering the overall yields of these sludge rials, moisture and water content, reaction temperature and time,
types, results apparently show that it would seem more beneficial microwave output power and type (multimode or monomodal),
to use primary sludge to produce biodiesel. Olkiewicz et al. (2012) reactor design/type, microwave receptors type, size, amount/con-
showed that profile comparison between primary, secondary and centration, catalyst type (if any) and concentration, mixing in-
blended sludge (from the same source) indicated no substantial tensity (stirring), type and flow rate of carrier gas.

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 5

In order to obtain the highest quality and conversion yields, biodiesel industry development is expected in fuel post-processing
these variables should be optimized on a case-by-case basis. (that is, upgrading extracted products to stable, standard-
Looking at Table 2, referred to pyrolysis technologies, it can be complying fuels) with a cost reduction expected to reach 90%
seen that anaerobically stabilized sludge, pyrolysed at different from 2009, and to a smaller degree (43%) in feedstock prices.
temperatures, shows oil yields up to 500  C that are in line with Therefore, from the data shown and hypothesizing exclusive use
those of blended and primary sludge in the transesterification of urban waste sludge as feedstock, which could be procured at the
process (greater at lower temperatures), but much higher than that mere cost of transportation (or even with an additional income
obtained from the same type of sludge with that process, while raw linked to a gate fee - it is, after all, a waste to be disposed of), thus
sludge (blended) achieves increasing yields with temperature up to assuming no feedstock costs, under the envisioned technological
an optimum of 550  C, where the yield is approximately twice that progress the cost a gallon of pyrolytic sludge-derived biodiesel
obtained by transesterification. In these two cases, feedstock should stabilize at around, or below, 1.5 $. This suggests that bio-
heating modalities between conventional and monomodal irradi- diesel production from sludge could be very profitable in the long
ation are most probably responsible for the difference in yield of run, especially considering that fossil oil is expected to increase in
the two processes, which may be studied and understood only with price in the long run.
very detailed studies, which are complicated by the fact that py- Studies have estimated that, using all annually available
rolysis processes duration is very short compared to extraction wastewater treatment plant sludge generated in the USA for con-
processes (in the order of minutes). Figs. 1 and 2 show, respectively, version to oil, 3.6  109 gallons (14  106 m3) of biodiesel could be
representative chromatograms of pyrolytic oil derived from urban produced, or about 1% of total US annual consumption (Dufreche
sludge by different researchers: Fig. 1 shows GC/MS analyses from et al., 2007). Considering that the expected 2020 EU sludge pro-
the same sludge sample MAP-processed at different temperatures duction is approximately double that of the USA, and using the
(Capodaglio et al., 2016c), while Fig. 2 shows results from two same conversion factors, it can be estimated that about 26  106 m3
sludge samples by Kwon et al. (2013). It can be seen that process of biodiesel could be produced in Europe annually (or about 15% of
temperature plays a substantial effect not only on overall biodiesel the overall traffic-related diesel demand, as of 2012). Additional
yield, but also in its properties. revenue from other pyrolysis-generated fractions is not discussed
in the cited studies.
3. Biodiesel economic considerations
4. Future directions in sewage sludge biodiesel production
Crude oil prices have been fluctuating between about 40 to
more than 140 US$ per barrel (1 barrel ¼ 31.5 gallons) in the last Considerable attention has been given recently to renewable
decade alone. As of 2010, the estimated cost of industrial produc- substitutes for fossil fuels, due to the concurrent problems of fossil
tion of biodiesel from dry sludge was $ 3.11 per gallon (1 fuel depletion, environmental degradation due to population in-
gal ¼ 3.875 L) of biodiesel, compared to $3.00 per gallon for fossil crease and waste amounts generation, and GHG emissions, linked
diesel (with crude sold at 78 US$/barrel). The biodiesel price was to global climate change. Governments and regulatory agencies
then broken down to $2.06/gal for preprocessing, extraction and worldwide are thus promoting the substitution of fossil fuels with
stabilization, and $1.05/gal for other miscellaneous process costs biofuels from various originating biomasses. Acceptance of the
(Kargbo, 2010). To be competitive, this needs to be reduced Kyoto protocol will lead to more global biodiesel production: it is
(without considering temporary incentives) to levels at or below anticipated that Kyoto-related policies will lead to a total bio-fuel
petroleum diesel costs: this objective may not be so far away. A demand in EU of around 30.3 million tons in 2020. With global
study from the US Dept. of Energy (DOE; Haq, 2012) estimated the human population increase, more land will be needed to produce
economic data pertaining to biodiesel production from agricultural food, thus food/energy competition could increase production costs
biomasses pyrolysis shown below (Table 3). of biodiesel plants, both edible and not. Such problem has already
The figures show that the most dramatic economic progress in emerged in Asia, where vegetable oil prices are relatively high. This

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
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 7

sludge conversion to biodiesel, and researches are trying to develop eere.energy.gov.


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