Journal of Analytical and Applied Pyrolysis 105 (2014) 108–115

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Journal of Analytical and Applied Pyrolysis

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

Characterization of the products from the pyrolysis of sewage sludge

in 1 kg/h rotating cylinder reactor
M.M. Pedroza a,∗ , J.F. Sousa a , G.E.G. Vieira b , M.B.D. Bezerra a
a
Departamento de Engenharia Química, Universidade Federal do Rio Grande do Norte (UFRN), Brazil
b
Departamento de Engenharia Ambiental, Instituto Federal do Tocantins (IFTO), Brazil

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

Article history: The objectives of this study were to produce and characterize bio-fuels through the thermal treatment of
Received 5 April 2013 sewage sludge in an 1 kg/h rotating cylinder reactor. The experimental procedure was divided into three
Accepted 16 October 2013 parts: (a) initial test using the temperatures of 450, 500, 550, 600 and 650 ◦ C while the nitrogen flow,
Available online 24 October 2013
the centrifuge rotation and biomass flow were kept constant, (b) 24–1 fractional experimental design
and (c) experiments exclusively for the characterization of gaseous fraction, using the temperatures
Keywords:
of 500, 550 and 600 ◦ C. The maximum liquid yield was 10.5% obtained at the temperature of 500 ◦ C,
Sewage sludge
inert gas of 200 mL/min, biomass flow of 22 g/min and centrifuge rotation of 20 Hz. The maximum char
Pyrolysis
Rotating cylinder reactor
yield was 61.9%, obtained at 500 ◦ C, inert gas of 100 mL/min, biomass flow of 4 g/min and centrifuge
Characterization rotation frequency of 20 Hz. The highest phase gas yield was 23.3%, obtained at 600 ◦ C, inert flow rate of
Bio-oil 200 mL/min, biomass flow rate of 22 g/min and rotation frequency of 30 Hz. The bio-oil had the following
Char characteristics: pH between 6.80 and 6.84, density between 1.05 g/mL and 1.09 g/mL, viscosity between
2.5 cSt and 3.1 cSt and high heating value between 16.91 MJ/kg and 17.85 MJ/kg. Non-oxygenated aliphatic
(55%) and aliphatic oxygenated hydrocarbons (27%) were found in the bio-oil. The main components
detected in the gas phase were H2 , CO, CO2 and CH4 . Hydrogen was the main constituent, with a yield
of 46.2% at 600 ◦ C. Among the hydrocarbons formed, methane was predominant (16.6%) at 500 ◦ C. The
results show that increasing the temperature from 500 to 600 ◦ C favors the increase in the gaseous phase
and reduction of solid and liquid fractions.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction reaction is endothermic and consists of basically heating the

The domestic sewage is a complex heterogeneous mixture of
organic and inorganic materials [1]. The solid sludge normally con-
tains 60–80% of organic matter, which is composed of 20–30% crude
protein, 6–35% fat and 8–15% carbohydrate [2]. Although sewage
sludge contains many valuable materials, it is often dismissed as
an undesirable residue. Mondala et al. [3] report that the lipid frac-
tion of this residue can be used for the production of biodiesel
through transesterification. Sewage sludge is formed by a variety of
functional groups (acids, alcohols, amines, amides, nitriles, ketones,
hydrocarbons). These organic structures have high energy potential
and can be converted into valuable fuels.
Several technologies, such as pyrolysis and gasification, have
been developed and represent viable alternatives to the use of
residual sludge. The pyrolysis has received greater attention in
recent years as an acceptable route for waste processing. The
∗ Corresponding author. Tel.: +55 84 99010402.
E-mail addresses: marciobarbalho@live.com, marciobarbalho@eq.ufrn.br
(M.M. Pedroza).
biomass (typically between 300 ◦ C and 600 ◦ C) in the absence of
air. During the process there is the formation of vapors (which are
condensed to produce a liquid that is usually indicated as bio-oil),
char and non-condensable gases (which can be used for heat and
energy to the process itself [4]).
Various kinds of biomass pyrolysis reactors have been reported
in the literature: fixed bed, fluidized bed, vortex and vacuum reac-
tors. Among these, the fluidized bed technology has stood out as
the best in bio-oil yield. In the present study, all experiments were
carried out in a rotating cylinder reactor. This kind of reactor has
the advantage of allowing control over the flow of biomass and the
rate of heat transfer.
The sludge used in this work was produced in an anaerobic
reactor (about 40 m3 /month) from an urban wastewater treatment
plant, located in Palmas, Brazil. This plant treats only domestic
sewage. Currently this material is dried in drying beds and exposed
to sunlight, at room temperature, and then disposed on land in
the vicinity of the treatment plant. This type of domestic sludge
disposal has the great disadvantage of the accumulation of heavy
metals, pathogenic microorganisms and toxic organic substances.
Sewage sludge is rich in volatile matter and can be converted into

0165-2370/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jaap.2013.10.009
 M.M. Pedroza et al. / Journal of Analytical and Applied Pyrolysis 105 (2014) 108–115 109

Table 1
Characteristics of the sewage.

Proximate analysis (%)

Moisture Volatile mattera Asha Fixed carbona
6.0 53.9 38.1 2.0

Ultimate analysis (%) Higher value (MJ/kg) Heating (HHV)

Cb Hb Nb Ob , c Sb 21.1
28.0 4.6 4.9 23.2 1.2

Metals (mg/kg)
Fe Zn Mn Cu Ni Cr Pb
28,911 891 82 219 24 39 47

Lignocellulosic materials (%)

Cellulose Hemicellulose Lignin
4.2 12.8 17.9
a
Dry basis.
b
Dry and ash free basis.
c
Calculated by difference.

usable energy sources. The objectives of the present work were to
produce bio-fuels through the thermal treatment of sewage sludge,
to characterize the products and to study experimentally the effects
of some operating conditions of the pyrolysis in a rotating cylinder
reactor in continuous mode.
2. Experimental
2.1. Biomass characterization
The residual sludge was supplied by an urban wastewater treat-
ment plant. The sludge was dried for 24 h at 103 ◦ C in a drying oven
and subsequently stored in an airtight container, crushed and then
sieved to fine pieces of about 0.5–1 mm to ensure sample homo-
geneity and to facilitate analytical procedures.
Chemical characteristics of the sludge are shown in Table 1.
Iron was found in large quantities (28,911 mg/kg). The high nitro-
gen content is typical in this kind of biomass, because it contains
residues of proteins and peptides coming from the microorgan-
isms used in digestion. The high heating value of the residue was
21.07 MJ/kg, higher than 16.5 MJ/kg given by Sanchez et al. [5],
possibly due to the higher content of volatile material.
The content of lignocellulosic material was 34.9%. Cellulose and
hemicellulose contents of 28% for undigested sludge and 14% for
digested sludge were found by Barneto et al. [6]. The presence of
lignocellulosic components in the sewage sludge is related to the
characteristics of the domestic sewage source. Higher levels of cel-
lulose and lignin are observed in sewage sludge from a population
whose diet is rich in fiber.
Crystalline structures were observed by scanning electron
microscopy (SEM) analysis. The micrographs show that the sam-
ple morphology has an irregular surface, with voids and openings.
The heterogeneity of the sample was best detected in the mag-
nifications of 1000× and 5000×. Microbial structures were also
observed, such as already dead bacteria, extracellular polymeric
substances and fungi that developed in the dried sludge after
digestion. Sewage sludge is a mixture of substances which are gen-
erally characterized by having minerals, colloids and particles from
decomposed organic matter, as shown in Fig. 1. The main miner-
als detected by X-ray diffraction were caolinite [Al2 Si2 O5 (OH)4 ],
quartz (SiO2 ), gibbsite [Al(OH)3 ], albite (NaAlSi3 O8 ), magnetite
(FeO.Fe2 O3 ), dolomite [CaMg(CO3 )2 ], muscovite [KAl2 Si3 AlO10
(OH,F)2 ], hematite (Fe2 O3 ) and rutile (TiO2 ).
The FTIR analyzes were performed to characterize the main
functional groups of the sewage sludge, as shown in Fig. 2. The
FTIR spectra interpretation was based on the work published by
Silverstein et al. [7].
At around 3300 cm−1 appears a broadband caused by the
stretching vibrations of the groups O H and N H. Two peaks
around 3000 cm−1 are typical of the axial deformation C H of
aliphatic structures (2980–2920 cm−1 ). A less intense band of
approximately 2300 cm−1 may be associated with the stretch-
ing vibration of nitrile functional group. The peak (1647 cm−1 ) is
placed around the frequency of stretching of the carbonyl amide
group (CONH, 1650–1550 cm−1 ). The amide functional group may
be present in the sewage sludge due the denaturation process of
microorganisms. This peak of 1647 cm−1 may also be associated to
the double bond of alkenes (1675–1645 cm−1 ) as well as aromatic
compounds (1600–1500 cm−1 ). The peak around 1550 cm−1 can
also be characteristic of aromatic compounds. Between 1300 cm−1
and 1500 cm−1 appears a peak that can be associated with the
functional groups CH2 and CH3 . This CH2 group can be found
in hydrocarbons and cellulose, which are typical components of
sewage sludge. Around 1250 cm−1 there is a small peak, which
may be due to the effect of angular deformation in the plane of
the groups O H and C O, present in carboxylic acids. In the fin-
gerprint, there are two bands between 1150 cm−1 and 1000 cm−1 .
The most important contribution to this peak would be a silicate
group (1080 cm−1 ). Sewage sludge consists mainly of components
of microorganisms, mainly bacteria (nucleic acids, proteins, car-
bohydrates and lipids), humic substances (endogenous residue)
formed during bacterial decomposition, undigested organic mate-
rial (cellulose) and inorganic material [8,9].
2.2. Pyrolysis unit
The pyrolysis unit developed as part of this research comprises
the following constituents: (a) biomass feeding system, (b) rotating
cylinder reactor, (c) solid separators, (e) column for vapor conden-
sation and (f) liquid collectors. The plant (Fig. 3) is designed to
process up to 1 kg of biomass/h.
The continuous feeding system consists of two silos. In the first
silo, a biomass mixer was installed to avoid agglomeration and in
the second silo, there is a helical spring. The spring is intended
to facilitate the biomass flow into the reactor and to avoid the
accumulation of solids thus avoiding clogging. The two silos are
connected by a volumetric screw system driven by an electric motor
with speed control. Nitrogen (3) was used to facilitate the flow of
pyrolytic gases and enhance heat transfer inside the reactor.
The stainless steel reactor (4) has a length of 100 cm and outer
diameter of 10 cm. The reactor is connected to an engine that pro-
motes rotation at 33.7 rpm. The reactor is heated at a constant
heating rate by a furnace (5). The solid material produced dur-
ing pyrolysis is retrieved in a solids separator (6). This separation
system consists of five cylindrical metal tubes, arranged in series,
110 M.M. Pedroza et al. / Journal of Analytical and Applied Pyrolysis 105 (2014) 108–115

Fig. 1. Microscopic image of sewage sludge with magnifications of: (a) 200, (b) 500, (c) 1000 and (d) 5000×.

1 .2
Si O
1 .0 N-H O-H
C C
O H
Abundance (UÅ)

0 .8
C-H
0 .6 C O

0 .4

0 .2
C N
0 .0
4000 3500 3000 2500 2000 1500 1000 500 0
-1
W a v e n u m b e r (c m )

Fig. 2. FTIR spectra of the sewage sludge.

heated by electric elements and isolated by glass wool blankets.

The separators surface temperature was set to 400 ◦ C.
The centrifuge (7) is located at the top of the vapor washing
column (8). All vapors condensed (9) are collected into stainless
steel reservoirs (10) with a volume of 0.5 L.

2.3. Experimental procedure

The experimental procedure in this study was divided into three

parts whose operating conditions are found in Table 2.
The rotation of the rotating cylinder reactor was 33.7 rpm for
all experiments. The biomass, previously dried at 70 ◦ C to remove
moisture, was fed into the reactor after the temperature reached
Fig. 3. Pyrolysis unit. the desired value. The operating conditions used in the fractional
experimental design are summarized in Table 3.
 M.M. Pedroza et al. / Journal of Analytical and Applied Pyrolysis 105 (2014) 108–115 111

Table 2
Operating conditions used in the pyrolysis of sewage sludge.

Parameters Initial tests with production of Fractional experimental design Production of bio-oil with
bio-oil characterization of the
non-condensable gaseous
phase

Temperature (◦ C) 450, 500, 550, 600 and 650 500 and 600 50, 550 and 600
Nitrogen gas flow (mL/min) 50 100 and 200 50, 75 and 100
Centrifuge rotation frequency (Hz) 25 20 and 30 20, 23 and 26
Biomass mass flow (g/min) 8 4 and 22 8

Table 3
Summary of operating conditions for the experiments.

Experiments Operating conditions

Temperature (◦ C) N2 flow rate (mL/min) Centrifuge rotation frequency (Hz) Biomass flow rate (g/min)

1 500 100 20 4
2 600 100 20 22
3 500 200 20 22
4 600 200 20 4
5 500 100 30 22
6 600 100 30 4
7 500 200 30 4
8 600 200 30 22

and biomass flow rate of 8 g/min. High pyrolysis temperatures

Fig. 4. Product yields of sewage sludge pyrolysis.
gave rise to high gas fraction yields. At 600 ◦ C the gas yield was
23.9 ± 0.6% while the liquid yield was 10.8 ± 0.2%, which can be
attributed to gasification and secondary cracking reactions of the
pyrolysis vapors. At all temperatures investigated, the amount of
water produced was much higher than the moisture content of
the raw material (6%), indicating that during pyrolysis, water is
formed in considerable amounts. The moisture content and par-
ticle size are the main variables associated with the characteristics
of the biomass and have great influence on the pyrolysis pro-
cess dynamics. The moisture content plays an important role in
the development of pyrolysis. In this case, the pyrolysis products
consisted of components with low molecular weight, especially
oxygenated ones. The water content has a major impact on the
power consumption during the drying of the biomass [10].

The liquid and solid products were collected for weighing and
3.2. Design of experiments
characterization. The bio-oil and aqueous fraction of the liquid were
continuously collected. In order to separate the aqueous and the
The experimental results obtained with the factorial design 24–1
organic fractions, dichloromethane was added. The aqueous frac-
are shown in Table 4. In this study, four factors (experimental vari-
tion was then separated from the organic fraction by decantation
ables) were investigated: temperature of the reactor (T), nitrogen
and weighed. The bio-oil density was measured with a glass pyc-
flow rate (QN2 ), centrifuge rotation frequency (Frot ) and biomass
nometer at 20 ◦ C. The samples viscosity was determined using a
flow rate (Qfeed ).
rheometer Thermo System Scientific, model Haake Mars Modular
The data from the factorial design 24–1 indicate that the tem-
Advanced Rheometer, at the temperature of 20 ◦ C. The pH of the liq-
perature affected negatively the liquid and solid fractions and
uid was determined by a pHmeter digital TECNAL, model 3 MP at
positively the gaseous fraction. The experimental results obtained
20 ◦ C. The liquid was dissolved in dichloromethane and analyzed
in this phase of the research show that increasing the temperature
by GC–MS using a Varian CP 3800. The gas phase was stored in
from 500 to 600 ◦ C favors the increase in the gaseous phase and
an air mattress and weighed for mass balance. The gas phase was
reduction of solid and liquid fractions yields.
sampled with portable gas cylinders and taken to be analyzed for
A decrease in the char yield with increasing temperature can
composition with an HP 5890 gas chromatograph equipped with a
be attributed to the devolatilization of organic solid compounds
TCD detector. The iron content in bio-oil and char were determined
(oil, humic acids, and proteins) and the partial gasification of the
by spectrometric analysis using an ICP-OES, model ICAP 6000.
carbonaceous char at high temperatures.
The contact between metals and organic matter may have
3. Results and discussion favored the devolatilization of organic compounds. The reactor
rotational speed may have helped the interactions between these
3.1. Product yields chemical constituents. Movements of shear and sliding of the
rotating cylinder reactor may favor biomass devolatilization as its
The yields of the pyrolysis products are shown in Fig. 4. Ini- dynamics favors gas–solid reactions. Important variables such as
tial tests were carried out under the following conditions: nitrogen rotation and inclination of the reactor can significantly decrease
flow rate of 50 mL/min, centrifuge rotation frequency of 25 Hz the residence time of pyrolytic vapors, favoring the pyrolysis.
112 M.M. Pedroza et al. / Journal of Analytical and Applied Pyrolysis 105 (2014) 108–115

Table 4
Product yields.

Expt. no. Operating conditions Yields (%)

T (◦ C) QN2 (mL/min) Frot (Hz) Qfeed (g/min) Char Bio-oil Gas Water

1 500 100 20 4 61.9 9.1 16.0 13.0

2 600 100 20 22 54.0 7.4 21.5 17.1
3 500 200 20 22 59.8 10.5 17.3 12.4
4 600 200 20 4 53.9 7.5 22.9 15.7
5 500 100 30 22 59.0 9.7 17.9 13.4
6 600 100 30 4 53.2 8.1 22.4 16.3
7 500 200 30 4 61.1 10.1 18.5 10.3
8 600 200 30 22 52.7 8.0 23.3 16.0

The cracking of tar, probably caused by the presence of dolomite Table 5

Bio-oil characterization.
in the sewage sludge, may have influenced the decrease in the
production of liquids, and as a result, favored the production of Properties Bio-oil from this research Other authors
gases.
LQ 1 LQ 2 LQ 3 [11] [4]
Pattiya [11] reported that the reduction of char yields with
pH (-) 6.16 5.09 6.81 7.90 –
increasing temperature could be due to the greater primary decom-
Density (g/mL) 1.09 1.08 1.05 1.10 0.98
position of the biomass at higher temperature and/or secondary Viscosity (20 ◦ C) (cSt) 2.5 3.0 3.1 17 –
thermal decomposition of the char formed before being entrained HHV (MJ/kg) 17.12 16.91 17.85 20.90 40.3
out of the reaction zone. The increase of gas yields with increasing Solid content (%) 0.84 0.94 0.87 0.12 –
temperature is possibly due to a combination of secondary thermal C (%) – 42.1 – 44.6 86.3
H (%) – 10.1 – 9.0 8.7
cracking of the evolved pyrolysis vapors and the char secondary O (%) – 40.0 – – –
decomposition. N (%) – 7.2 – 7.5 3.6
In the present work, the highest char yield (61.9%) was observed S (%) – 0.6 – 0.7 –
under the following conditions: reactor temperature of 500 ◦ C, Legend: LQ1 − T = 500 ◦ C, QN2 = 50 mL/min and Frot = 20 Hz; LQ2 − T = 550 ◦ C, QN2
nitrogen flow rate of 100 mL/min, centrifuge rotation frequency of = 100 mL/min and Frot = 26 Hz; LQ3 − T = 600 ◦ C, QN2 = 100 mL/min and Frot = 23 Hz;
20 Hz and biomass flow rate of 4 g/min. The lowest yield (52.7%) was Fonts et al. [11] – obtained in fluidized bed reactor at 530 ◦ C and QN2 = 4.5 L/min;
obtained at 600 ◦ C, nitrogen flow rate of 200 mL/min; centrifuge Vieira et al. [4] – obtained in fixed bed reactor at 380 ◦ C.

rotation frequency of 30 Hz and biomass flow rate of 22 g/min.

The maximum yield of bio-oil was approximately 10.5%. This
experiment was performed at 500 ◦ C, centrifuge rotation frequency
of 20 Hz, nitrogen flow rate of 200 mL/min and biomass flow rate of
22 g/min. For these conditions the water yield was approximately
12.4% (using dichloromethane to separate the water from the bio-
oil), indicating low water content in the bio-oil. The lowest bio-oil
yield was 7.4% obtained at 600 ◦ C, centrifuge rotation frequency of
20 Hz, nitrogen flow rate of 100 mL/min and biomass flow rate of
22 g/min, as shown in Table 4. It is observed that higher tempera-
tures and lower nitrogen flow rates result in greater degradation of
vapors and increases the production of non-condensable gases.
3.3. Bio-oil analysis
3.3.1. Physicochemical properties
The results of the viscosity, density, pH, calorific value and ele-
mental analysis of bio-oil are shown in Table 5.
The pH of bio-oil obtained in this study was around neutral-
ity (6.81 for LQ3) and significantly different from the typical pH
of lignocellulosic pyrolytic oils (pH between 2 and 3) [12]. One
possible explanation for this behavior is the presence of nitrogen
compounds and phenol, which is known to be a weak acid with a
pH around 5.5 in dilute solutions, in the liquid.
The density of the bio-oil, which is related to the water con-
tent, varied between 1.05 g/mL and 1.09 g/mL. Fonts et al. [12] and
Oasmaa [13] reported values between 1.2 g/mL to 1.3 g/mL.
The viscosity values were between 2.5 cSt and 3.1 cSt. These
results are well below those reported by Fonts el al. [12] and other
researchers [8], 17 and 7.92 ± 3.04 cSt, respectively. The low viscos-
ity values of the samples of bio-oil obtained in this study may be
associated with not only the presence of water in the liquid but also
the short period of time between collection and analysis. The sam-
ples were analyzed immediately after the experiments, minimizing
polymerization reactions.
The main problems associated with the use of bio-oil as fuel are
low volatility, high viscosity, coking and corrosion. Although these
problems limit the use of bio-oil in static applications, the bio-oil
has been successfully used in boilers and has shown potential for
use in diesel engines and turbines [14].
The oxygen content is the main reason for the differences
between the properties observed between hydrocarbon fuels and
oils derived from the pyrolysis of biomass [15]. The oxygen content,
obtained by the difference in the elemental analysis of bio-oil, was
40% (sample LQ2). High oxygen contents in the oil lead to instabil-
ity due to polymerization reactions, which increases the viscosity
and decreases the market value of the oil [16].
The HHV of bio-oil varied between 16.91 MJ/kg and 17.85 MJ/kg.
Oasmaa et al. [17] reported values between 13 MJ/kg and 18 MJ/kg.
Other authors [18] obtained 36.42 MJ/kg for the bio-oil produced
from aerobic activated sludge. According to the authors, the aerobic
sludge contains higher carbon content if compared to the anaero-
bically digested sludge, which gives higher HHV values. Vieira et al.
[4] investigated the pyrolysis of petrochemical sludge; the resulting
oil had an HHV of 40.30 MJ/kg.
The solids content in the bio-oil samples ranged from 0.84%
(LQ1) and 0.94% (LQ2). Lower centrifugation frequency (20 Hz) led
to lower solids content, which indicates that the centrifugation pro-
cess also influences the entrainment of solids during the reaction.
Oasmaa et al. [17] reported that the biomass composition and the
vapors condensation system also influences the solids content of
the final bio-oil.
3.3.2. Chromatographic analysis
The area of the peaks of the functional groups of the bio-oil is
shown in Fig. 5. The liquid was obtained under the following condi-
tions: temperature of 550 ◦ C, nitrogen flow rate of 100 mL/min and
centrifuge rotation frequency of 23 Hz.
Results show that the bio-oil studied consisted of many chem-
ical compounds, such as aliphatic, monoaromatic, polyaromatic
 M.M. Pedroza et al. / Journal of Analytical and Applied Pyrolysis 105 (2014) 108–115
Table 6
Immediate analysis and calorific values of char.
Char (present research)
Sample 1 Sample 2
Moisture (%) 9.2 8.9
Ash (%) 68.7 70.3
Volatile material (%) 18.1 17.9
Fixed carbon (%) 4.0 2.9
Carbon (%) – 15.1
Hydrogen (%) – 2.2
Nitrogen (%) – 3.2
High heating value (MJ/kg) 5.9 5.6
Sample 1: T = 500 ◦ C, QN2 = 50 mL/min, Frot = 20 Hz; sample 2: T = 500 ◦ C, QN2 = 100 mL/min, Frot = 30 Hz; sample 3: T = 600 ◦ C, QN2 = 100 mL/min, Frot = 20 Hz, Pokorna et al. [20]:
T = 500 ◦ C, QN2 = 140 mL/min, anaerobic sludge in semi-continuous reactor; Hossain et al. [21]: T = 550 ◦ C using sludge digested in fixed bed reactor.
Fig. 5. Areas of the functional groups of the bio-oil.
and long chain hydrocarbons (e.g. benzene, xylene, 1-alkenes, n-
alkanes and their methyl derivatives, with carbon chains ranging
from C6 to C26 ), carboxylic acids of small and long chains, aldehydes,
ketones, nitriles, long chain esters and alcohols, ethers, amides
and amines. The oxygenated compounds consisted of aliphatic car-
boxylic acids (RCOOH), esters (RCOOR ) and ethers. Nitrogenous
compounds found were amines and amides (RCONH2 ), where R and
R are long aliphatic chains with 12, 14, 16 and 18 carbon atoms.
Cholestene, alkylcholestene colestenol, phenols, acids, aldehydes
and ketones were also identified. The halogenated constituents
consisted of molecules containing fluorine, chlorine and bromine.
Sulfur was identified as 2-methyl, 2-undecanethiol, or C12 H26 S.
The nitrogen and oxygen compounds identified in bio-oil are
associated with the reactions of thermal degradation of denatured
proteins of microorganisms present in sewage sludge. Zhang et al.
[18] stated that the mechanisms observed during the pyrolysis of
waste sludge are: (1) decomposition of aliphatic compounds, (2)
breaking of protein peptide bonds and (3) esterification of car-
boxylic acids.
The decarboxylation and decarbonylation reactions of fatty
acids present in the sludge may have formed aliphatic and aliphatic-
oxygenated hydrocarbons. The decarboxylation also may have
produced alkanes and carbon dioxide, while the decarbonylation
reaction produced alkenes, water and carbon monoxide. Fonts et al.
[8] investigated the pyrolysis of sewage sludge using an anaer-
obic fluidized bed at 550 ◦ C and determined high concentrations
of steroids (25%) and aliphatic hydrocarbons (23%) in the bio-oil.
According to the authors, these compounds are derived from the
thermal degradation of lipids present in the biomass. Shen and
Zhang [19] studied the pyrolysis oil obtained from the sewage
sludge from a fluidized bed using GC–MS. According to the authors,
the structure of the bio-oil is composed of aromatic groups with
113
Other authors
Sample 3 [20] [21]
8.5 – 1.0
65.2 – 81.8
22.5 – 15.3
3.8 – 1.9
– 24.5 16.2
– 12.1 0.54
– 19.8 1.84
5.8 5.2 –
one to three aromatic rings connected by long-chain hydrocarbons
containing hydroxyl groups.
The oxygen monoaromatic compounds (4.15%) were identified
in greater quantity than those non-oxygenated (2%). The forma-
tion of the monoaromatic compounds can be explained by the
Diels–Alder reaction. Butadiene could combine with either ethyl-
ene or propylene available to produce such substances.
The 2-methyl-9,10-anthracenedione was only polycyclic aro-
matic compound identified in bio-oil. Mechanisms of the
Diels–Alder reactions have been suggested by several authors
to explain the formation of polyaromatic hydrocarbons in the
pyrolysis of biomass, via dehydrogenation of alkenes and dienes,
cyclization and subsequent aromatization. Sanchez et al. [5]
reported that the temperature of the pyrolytic process of domestic
sewage is a variable that interferes with the formation of polycyclic
aromatic hydrocarbons. The authors demonstrated in previous
studies that the quantities of these compounds were negligible at
temperatures below 500 ◦ C, and observed a substantial increase in
the concentration of polyaromatic at temperatures above 700 ◦ C.
The phenolic compounds found in the bio-oil produced in the
rotating cylinder reactor were the following: phenol, 2-methyl
phenol, 2-methoxy phenol, 4-methyl phenol, 2,4-dimethyl phe-
nol, 2-methoxy-4-methyl phenol, 4-ethyl-2-methoxy phenol, 2,6
dimethoxy phenol and 2-methoxy 4-(1-propenyl) phenol. These
compounds are widely used in chemical industry. The primary use
of phenol is associated with the production of phenolic resins which
are used in the construction of plywood, automotive and appliance
industries. Phenol is also used in the production of intermediate
products from the manufacture of nylon and epoxy resins. Due
to its antiseptic action, it can also be used in the production of
disinfectants and personal hygiene products.
3.4. Char characterization
The contents of moisture, volatile material, ash and fixed carbon
of the char samples obtained from the pyrolysis of sewage sludge
in the rotary cylinder are presented in Table 6.
The volatile material content of sample 3 can be associated with
the presence of bio-oil in the char. Part of this oil condenses in the
separators due to low temperatures.
The content of metals in the char is shown in Table 7. A great
amount of iron was found in sample 3 due to the high tempera-
ture (600 ◦ C) that promotes sublimation of organic molecules thus
increases the content of solids.
Hwang et al. [22] carried out the pyrolysis of sewage sludge
at 500 ◦ C and determined the following concentrations of metals
in char: cadmium (5.5 mg/kg), chromium (70.7 mg/kg), lead
(97.6 mg/kg), zinc (1593 mg/kg), copper (70.2 mg/kg), potassium
(3434 mg/kg), sodium (2140 mg/kg) and magnesium (5473 mg/kg).
Hossain et al. [21] characterized the char obtained from domes-
tic residual sludge at 550 ◦ C using a fixed bed reactor. The main
114 M.M. Pedroza et al. / Journal of Analytical and Applied Pyrolysis 105 (2014) 108–115

Table 7
Average value and standard deviation of metals content.

Metal (mg/kg) Char

Sample 1 Sample 2 Sample 3

Zn 1338 ± 56 1208 ± 42 1286 ± 45

Cd ND ND ND
Mn 119 ± 5 107 ± 7 ND
Pb ND 42.2 ± 5 ND
Cu 312 ± 12 236 ± 15 242 ± 9
Ni 67.0 ± 6 48.5 ± 4 47.6 ± 8
Cr 91.2 ± 4 64.8 ± 5 65.4 ± 3
Fe 42,842 ± 84 39,466 ± 76 48,623 ± 91

Sludge sample: 600g

mgFe/kg sludge: 28911
Mass of iron in sludge (mg) = Fig. 7. Composition of the gas phase obtained during the pyrolysis of sewage sludge.
(28911mgFe/kg sludge)×(600g sludge)/1000=17347

Bio-oil yield = 9.7% Char yield = 59% mostly contaminated with chlorinated substances (trichloroethy-
lene and/or perchloroethylene) as well as with heavy metals
mgFe/kg bio-oil = 680 mgFe/kg char = 39466 (chromium or lead) or organochlorine pesticides (lindane or DDT)
% (w/w) Fe = 0.068 % (w/w) Fe = 3.95 [25]. Iron is also employed in the process of removing pollutants in
effluents by photo-Fenton oxidative processes [26].

Mass of iron in bio-oil (mg) = Mass of iron in char (mg) =

(680mgFe/kg bio-oil)×0.097×(600g (39466 mgFe/kg char)×0.59×(600g
sludge)/1000 = 39 Sludge)/1000 = 13971
Total mass of iron = 39 + 13971 = 14011
Recovery of iron = (14011/17347)×100 = 80.75%
Fig. 6. Estimates of the percentages of iron transferred from biomass to bio-oil and
char during pyrolysis of sewage sludge.
metals detected were the following: arsenic (5.9 mg/kg), boron
(13.0 mg/kg), barium (230 mg/kg), cobalt (13 mg/kg), chromium
(130 mg/kg) copper (800 mg/kg), manganese (940 mg/kg), nickel
(160 mg/kg) and zinc (890 mg/kg).
Beneficial effects of char to increase the crop yield and soil
properties have been published [23]. However, there is limited
information about the properties of the char produced by pyrolysis
of wastewater sludge [21].
Char has also been used as adsorbent material. Liu et al. [24]
studied the removal of tetracycline from aqueous solutions using
pyrolytic char modified with KOH. The results show that the alkali
treated char possesses larger surface area than raw char and
exhibits an excellent adsorption performance (58.8 mg/g), which
implies these materials can be extended to the treatment of indus-
trial effluents.
3.5. Iron mass balance
Under the conditions T = 500 ◦ C, QN2 = 100 mL/min and
Frot = 30 Hz, a mass balance was performed to evaluate the
amount of iron transferred during the reaction for bio-oil and char.
The results are presented in Fig. 6. The contents of metal found in
bio-oil and char were 680 and 39,466.8 mgFe/kg, respectively. This
means 80.75% of the iron was transferred from biomass to bio-oil
and char and the rest was dragged with the non-condensable
gases.
The presence of metals in the char points to a possible applica-
tion of iron in the processing of degraded environments. Iron has
been applied in the removal of chlorinated organic compounds in
soils. Zero-valent iron has been applied for the treatment of water,
wastewater, groundwater, soil, sediments and gaseous streams,
3.6. Non-condensable gas phase characterization
The components detected (by GC/FID/TCD) in the non-
condensable gaseous phase were: hydrogen (H2 ), carbon monoxide
(CO), carbon dioxide (CO2 ), methane (CH4 ) and light weight hydro-
carbons (C2 , C3 , C4 , C5 and C6 ), as shown in Fig. 7.
The highest hydrogen content was 45%, obtained under the
following conditions: temperature of 600 ◦ C, nitrogen flow rate
of 100 mL/min and centrifuge rotation frequency of 26 Hz. The
results also show a linear increase in the content of the gas as
the temperature increases. One possible explanation for this is
that high temperatures favored the dehydrogenation reaction of
heavy hydrocarbons, leading to an increase in H2 . Additionally,
H2 can be considered a good indicator for secondary cracking of
the vapors during the pyrolytic process. Another possibility is that
the initial moisture content of biomass used may have generated
an atmosphere rich in steam at high temperatures. Water reacts
with carbon monoxide (water–gas-shift reaction), giving rise to
endothermic reactions and favoring the generation of H2 .
The biomass used in this study has high ash content. The metals
contained in the ash, especially iron, can catalyze dehydrogenation,
which also favors the formation of H2 [27].
Secondary reactions, in particular, aromatization, are also
responsible for the formation of hydrogen, especially when the
residence time of vapors is higher than expected.
The concentration of CO and CO2 ranged from 8.18 to 15.3%
and 24.4 to 32%, respectively. Mechanisms of formation of these
two gases during pyrolysis involve cracking, decarboxylation and
biomass decarbonylation. As observed by other authors, CO and
CO2 are formed by thermal decomposition of oxygenated organic
compounds (lipids, carbohydrates, cellulose and lignin) and from
the decomposition of inorganic salts such as carbonates [24].
The mixture H2 + CO (synthesis gas) represented 56% of the gas
phase under the following conditions: temperature of 600 ◦ C, nitro-
gen flow rate of 100 mL/min and centrifuge rotation frequency of
20 Hz. Zhang et al. [18] reported the values between 40% and 55% for
the synthesis gas obtained from pyrolysis of sewage sludge using
a tubular reactor in a batch system at the temperatures of 600 and
700 ◦ C, respectively.
Fig. 7 shows similar behavior for the composition of CO2 at the
temperatures of 500 and 550 ◦ C (27.3%). According to Shen and
Zhang [19], the thermal degradation of the carboxylic group occurs
 M.M. Pedroza et al. / Journal of Analytical and Applied Pyrolysis 105 (2014) 108–115
between 160 ◦ C and 600 ◦ C and is intensified at temperatures above
550 ◦ C.
Although C4 , C5 and C6 were detected in some experiments, the
majority of hydrocarbons found consisted of CH4 , C2 H2 , C2 H4 , and
C3 H8 . Methane was found in greater quantity, with a concentra-
tion of 16.6% at 500 ◦ C and 7.7% at 600 ◦ C. This same behavior was
observed for C2 and C3 as shown in Fig. 7.
The calorific value of the gas phase, calculated using the ISO
6976:1995, was influenced by the evolution of hydrocarbons dur-
ing the pyrolysis. The highest calorific value obtained in this study
was 14,380 kJ/m3 when the pyrolytic system was operated at
500 ◦ C, with rotation frequency of 20 Hz and nitrogen flow rate of
50 mL/min. Inguanzo et al. [28] investigated the pyrolysis of anaer-
obic sludge using a batch reactor and determined that, at 455 ◦ C,
the gaseous fraction had the highest calorific value (17,000 kJ/m3 ),
an effect caused by the release of the constituents C2 H4 and C2 H6
into the gas phase.
4. Conclusions
High pyrolysis temperatures decreases the yields of the liq-
uid and solid fractions, and increases the yield of gas phase. It
is observed that high temperatures, high centrifuge rotation fre-
quency and low nitrogen flow rate, combined, provide a more
efficient degradation of the pyrolytic vapors into smaller molecules,
thus increasing the production of gases. The bio-oil obtained using
the rotating cylinder reactor had a high content of aliphatic sub-
stances. The paraffinic and olefinic compounds in the bio-oil can
be used as fuel. The resulting oil can be co-processed to reduce the
content of oxygen, thus increasing H/C molar ratios. Hydrogen was
the most abundant component at high temperatures in the non-
condensable gas phase. The mixture H2 + CO (synthesis gas), with a
concentration of 56%, was obtained at 600 ◦ C. The gaseous products
obtained had a high calorific value (14,380 kJ/m3 ).
Acknowledgments
The authors would like to thank the Brazilian Agência Nacional
de Petróleo (ANP) – National Agency of Petroleum, Natural Gas
and bio-fuels, Conselho Nacional de Desenvolvimento Cientifico e
Tecnológico (CNPq), CAPES and FINEP, for the financial support.
115
References
[1] Metcalf, Eddy, Wastewater Engineering Treatment Disposal and Reuse, 4th ed.,
McGraw-Hill, New York, NY, 2002.
[2] W.W. Eckenfelder, Industrial Water Pollution Control, McGraw-Hill, Boston,
MA, 2000.
[3] A. Mondala, K. Liang, H. Toghiani, R. Hernandez, T. French, Bioresource Tech-
nology 100 (2009) 36.
[4] G.E.G. Vieira, G.A. Romeiro, S.M. Sella, R.N. Damasceno, R.G. Pereira, Bioresource
Technology 100 (2009) 7.
[5] M.E. Sanchez, J.A. Menéndez, A. Domínguez, J.J. Pis, O. Martínez, L.F. Calvo, P.L.
Bernad, Biomass and Bionergy 33 (2009) 13.
[6] A.G. Barneto, J.A. Carmona, J.E.M. Alfonso, J.D. Blanco, Journal of Analytical and
Applied Pyrolysis 86 (2009) 7.
[7] R.M. Silverstein, X. Francis, J. David, Identificação Espectrométrica de Compos-
tos Orgânicos, Editora LTC, 7th ed., 2007.
[8] I. Fonts, M. Azuara, G. Gea, M.B. Murillo, Journal of Analytical and Applied
Pyrolysis 85 (2009) 23.
[9] M.M. Pedroza, G.E.G. Vieira, J.F. Sousa, Ingeniería y Ciencias Ambientales: Inves-
tigación, Desarrollo y Práctica 4 (2011) 2.
[10] J.L. Shie, J.P. Lin, C.Y. Chang, D.J. Lee, C.H. Wu, Resources, Conservation and
Recycling 39 (2003) 15.
[11] A. Pattiya, Bioresource Technology 102 (2011) 2.
[12] I. Fonts, E. Kuoppala, A. Oasmaa, Energy & Fuels 23 (2009) 1.
[13] A. Oasmaa, C. Peacocke, A Guide to Physical Property Characterisation of
Biomass–Derived Fast Pyrolysis Liquids, VTT Publications, Technical Research
Centre of Finland, 2001.
[14] S. Czernik, A.V. Bridgwater, Energy & Fuels 18 (2004) 370.
[15] J.P. Diebold, A Review of the Chemical and Physical Mechanisms of the Stor-
age Stability of Fast Pyrolysis Bio-Oils, Golden, Colorado, Nacional Renewable
Energy Laboratory, 2000.
[16] V.A. Doshi, H.B. Vuthaluru, T. Bastow, Fuel Processing Technology 86 (2005) 26.
[17] A. Oasmaa, M. Kytoë, K. Sipilaë, Pyrolysis oil combustion tests in an industrial
boiler, in: Progress in Thermochemical Biomass Conversion, Blackwell Science,
Oxford, UK, 2001.
[18] B. Zhang, S. Xiong, B. Xiao, D. Yu, X. Jia, International Journal of Hydrogen Energy
36 (2011) 7.
[19] L. Shen, D. Zhang, Fuel 82 (2003) 57.
[20] E. Pokorna, N. Postelmans, P. Jenicek, S. Schreurs, R. Carleer, J. Yperman, Fuel
88 (2009) 3.
[21] M.K. Hossain, V. Strezov, P.F. Nelson, Journal of Analytical and Applied Pyrolysis
85 (2009) 12.
[22] I.H. Hwang, Y. Ouchi, T. Matsuto, Chemosphere 68 (2007) 19.
[23] B. Glaser, J. Lehmann, W. Zech, Biology and Fertility of Soils 35 (2002) 219.
[24] P. Liu, W.J. Liu, H. Jiang, J.J. Chen, W.W. Li, H.Q. Yu, Bioresource Technology 121
(2012) 1.
[25] S. Machado, S.L. Pinto, J.P. Grosso, H.P.A. Nouws, J.T. Albergaria, C. Delerue-
Matos, Science of the Total Environment 445–446 (2013) 1.
[26] C. Mendoza-Marín, P. Osorio, N. Benítez, Journal of Hazardous Materials 177
(2010) 12.
[27] S.A. Scott, J.S. Dennis, J.F. Davidson, A.N. Hayhurst, Fuel 85 (2006) 35.
[28] M. Inguanzo, A. Dominguez, J.A. Menéndez, C.G. Blanco, J.J. Pis, Journal of Ana-
lytical and Applied Pyrolysis 63 (2002) 91.