Waste Management 78 (2018) 217–226

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

High temperature pyrolysis of sewage sludge as a sustainable process for

energy recovery
C. Karaca a, S. Sözen a,b,⇑, D. Orhon a,c, H. Okutan d
a
ENVIS Energy and Environmental Systems R&D Ltd, ITU Arı Teknokent, Arı-1 Building No. 16, 34469 Maslak, Istanbul, Turkey
b
Faculty of Civil Engineering, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey
c
Civil Engineering Department, Near East University, Nicosia, North Cyprus
d
Faculty of Chemical and Metallurgical Engineering, Chemical Engineering Processing Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey

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

Article history: This study explored the potential of high temperature pyrolysis for energy recovery from domestic sew-
Received 8 December 2017 age. It mainly defines optimum operating conditions to maximize syngas generation. A pyrolysis unit was
Revised 14 May 2018 operated in batch mode, at temperatures of 450, 600 and 850 °C, rotation speeds of 10, 40 and 60 Hz. The
Accepted 18 May 2018
sludge had 6% moisture content; it contained 65% organic matter and involved a low calorific value of
Available online 7 June 2018
13.535 kJ/kg dry matter. Pyrolysis at 850 °C and high rotation speed of 60 Hz yielded the highest conver-
sion of sludge to syngas, with an average of 59% of the organic matter as syngas, 29% as tar and 12% as
Keywords:
biochar. Pyrolysis enabled 74% of the energy recovery as syngas and tar. Continuous full-scale pyrolysis
Sewage sludge
High rate pyrolysis
systems would further increase the syngas by recovering condensable gaseous products and/or recycling
Syngas tar back into the pyrolysis unit. A unified approach for energy recovery management should equally con-
Thermal conversion sider what fraction of the energy contained in the wastewater was consumed and wasted before gener-
Energy recovery ating the sludge. Therefore, the adopted management scheme should also cover all design and operation
parameters of the treatment plant, because this is how the energy is best conserved even before the
sludge is generated.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction for low technology disposal and reuse practice. While landfilling
is still implemented for the major portion of municipal sludge in
In recent years, there has been a major shift in research efforts EU countries, related regulations aim to minimize landfilling (EC,
towards sustainable sludge management. The driving force of this 1999); they now include constraints that may totally prohibit land-
shift was the ever-increasing cost of sludge disposal, accounting for fill applications rather than trying to reduce its adverse effects on
a major fraction of the total cost of wastewater treatment (Wei the environment (Sözen et al., 2015). Similarly, reuse in agriculture
et al., 2003). Therefore, the traditional approach primarily focused is also advocated as a beneficial option for municipal sludge and
on minimizing sludge generation: a number of physical and chem- practiced to a limited extent (Lederer and Rechberger, 2010). How-
ical methods have been suggested to reduce the sludge generation ever, this is now estimated to be a much more sensitive disposal
potential of conventional treatment processes (Odegaard, 2004). route as compared to landfilling, due to potential health risks
Earlier studies attempted reducing sludge production by operating (Horn et al., 2003; Hospido et al., 2010).
biological treatment plants at high sludge retention times as Increasing concerns and stringent limitations on traditional
extended aeration systems; this mode decreased the amount of sludge disposal practice diverted the major interest towards the
sludge but required excessive aeration (Orhon, 2015). Recently, energy content of waste material, regarding sludge as an energy
new activated sludge modifications, such as the OSA process, have resource. The possibility of recovering this energy also affected
been developed to provide substantial reductions in sludge pro- the conventional biological treatment, which tends to minimize
duction (Novak et al., 2007; Chon et al., 2011; Yagci et al., 2015). generated excess sludge at the expense of additional energy for
Sludge management was also affected by the growing concern stabilization. The energy recovery concept modified the biological
treatment practice towards high rate systems enabling to harvest
the maximum possible level of sludge for energy recovery. Studies
⇑ Corresponding author at: Faculty of Civil Engineering, Environmental Engineer- have shown that a membrane bioreactor system operated at extre-
ing Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey.
mely low sludge ages would provide optimum energy conservation
E-mail address: [email protected] (S. Sözen).

https://doi.org/10.1016/j.wasman.2018.05.034
0956-053X/Ó 2018 Elsevier Ltd. All rights reserved.
218 C. Karaca et al. / Waste Management 78 (2018) 217–226

Nomenclature

A2O anaerobic-anoxic-oxic process OMF organic matter fraction

ASM activated sludge model OSA oxic-settling-anaerobic
ASTM American Society for Testing and Materials RPM revolutions per minute
COD chemical oxygen demand SFMBR super-fast membrane bioreactors
CV calorific value VSS volatile suspended solids
DM dry matter WWTP wastewater treatment plant
HHV higher heating value
LHV lower heating value

in the sludge also including particulate COD entrapped onto bio- rized in Karaca et al. (2015), similar studies (Dominguez, 2006;
mass, while removing soluble COD and securing an effluent quality Dominguez et al., 2008; Fonts et al., 2009; Zhang et al., 2011;
suitable for reuse (Basßaran et al., 2012; Sözen et al., 2016). Studies Pedroza et al., 2014; Ospanov et al., 2015) were conducted to
estimated the energy equivalent of the organic matter (COD) in explore the energy recovery potential of pyrolysis from sewage
wastewater in the narrow range of 13.807–14.895 kJ/kg COD sludge. As it will be analyzed in the following sections of the paper,
(Heidrich et al., 2011; McCarty et al., 2011). Depending on the type these studies, although useful, were conducted as random research
of selected biological treatment scheme, a fraction of this energy is efforts, lacking the basic information for a unified evaluation. In
transferred to generated sludge. The novel energy recovery concept this context, this work was basically focused on recognizing all
should be designed to increase this fraction and to maximize the necessary parameters for defining a unified basis of high tem-
energy recovery by novel processes (Garrido et al., 2013). perature pyrolysis of sewage sludge mainly aiming at syngas gen-
Anaerobic digestion is the traditional biochemical extension of eration, emphasizing the influence of temperature and rotation
conventional wastewater treatment for energy recovery, where speed on the composition of syngas. The results were compared
biogas is obtained at the expense of partial biodegradation of the with the expected outputs of anaerobic digestion based on com-
organic matter in sludge. Biogas recovery was first practiced in parison of the respective energy generation levels.
1985, 20 years earlier than the discovery of activated sludge pro-
cess, using the primitive version of anaerobic digestion (Bushwell, 2. Materials and methods
1957). While biogas generation is useful, the process is quite inef-
fective: It only breaks down 35–50% of the COD/VSS in sludge and 2.1. Experimental rationale
converts it into methane; it leaves behind a highly diluted, half sta-
bilized sludge, which needs to be processed before final disposal The experimental study was designed to determine the energy
(Svardal and Kroiss, 2011; Bolzonella et al., 2012). Aside from recovery potential of high temperature pyrolysis from sewage
anaerobic digestion, energy recovery can also be accomplished by sludge; it essentially aimed to uncover conditions that would max-
means of thermochemical processes, which include a range of imize syngas generation, a product quite suitable to be used as a
technologies including gasification, pyrolysis, reforming and potential renewable energy supply that would replace natural
hydrothermal conversion, aiming to obtain similar end products, gas after appropriate treatment. A laboratory scale pyrolysis sys-
but often involve a series of chemical transformations (Luque tem designed for batch mode operation was used for this purpose.
et al., 2012). The energy recovery achieved in the pyrolysis unit was evaluated
Pyrolysis is one of the innovative technologies that has been in terms of solid (biochar), liquid (tar) and gas (syngas) components
extensively investigated and implemented in the past decades to obtained at the end of batch operation; the variation in the relative
recover energy from a wide range waste material ranging from magnitude of these components was observed as a function of
feedstock; organic residues to plastics and many others (Fytili selected operation conditions. In this study, pyrolysis temperature
and Zabaniotou, 2008; Basu, 2010; Antoniou and Zabaniotou, and rotation speed were chosen as the major parameters to deter-
2013; Miandad et al., 2016a, 2016b, 2017a, 2017b). Briefly, the mine the diversity of the products. The applied ranges for these
pyrolysis process involves heating and holding biomass for a spec- two parameters were selected based on practical experience
ified time in the absence of oxygen, to disintegrate into various reported in the literature (Dümpelmann et al., 1991). The rotation
energy–rich products; the principle products are commonly speed was chosen to have a homogenous mixture in the system.
defined as syngas (CO, H2, CO2, CH4); tar, also known as bio-oil The system should be well mixed in order to see how the sample
(organic compounds with low volatility mixed with water) and thermally cracked within different temperatures. The system tem-
biochar, the solid by-product. Depending on the selected pyrolysis perature was sequentially set at 450 °C, 600 °C, and 850 °C to rep-
temperature, the nature and composition of products may be chan- resent the conditions for the low, medium and high temperature
ged. Most of the early studies were focused on flash pyrolysis at pyrolysis (Inguanzo et al., 2002; Dominguez 2006; Ospanov et al.,
medium temperature to maximize bio-oil production (Scott et al., 2015;). A similar approach was also accepted for the rotation
1985; Piskorz et al., 1986; Yaman, 2004; Dominguez et al., 2005; speed, where 600 rpm, 2400 rpm and 3600 rpm were applied
Fonts et al., 2009; Zaimes et al., 2015). Aside the temperature, there (Wagenaar et al., 1993; Pedroza et al., 2014; Liu et al., 2018). Rota-
are many parameters such as particle size, heating rate, residence tion speed defines the number of turns of the pyrolysis reactor by
time, and rotation speed in case of using a rotating reactor, which time as revolutions per minute (1 rpm = 0.016 Hz) so the selected
would affect the yield of the ultimate products along the process rotation speeds were identified as 10 Hz, 40 Hz and 60 Hz through
(Basu, 2010). the paper.
This study was basically conducted to evaluate and propose
high temperature pyrolysis as a promising energy recovery alter- 2.2. Experimental set-up
native to the traditional anaerobic digestion of sludge. Essentially,
this technology is not so widely applied at industrial level, espe- Dried sludge was subjected to pyrolysis in an electrically heated
cially not for sludge generated by sewage treatment. As summa- rotary kiln pyrolysis system. The rotary kiln pyrolysis set-up was
 C. Karaca et al. / Waste Management 78 (2018) 217–226 219

manufactured by one of the local construction firm (IET Engineer- four runs (Run 1, 4, 5, 8). Each run was duplicated under the same
ing). The system included (1) electrical heating furnace, (2) stain- conditions to justify the results. The results were close to each
less steel reactor, (3) automated pyrolysis chamber, (4) gas other in each duplicated experiments (2–4% variation).
outlet, (5) tar outlet, (6) flare, (7) thermocouple of heater cabin,
(8) thermocouple of gas pipe and (9) thermocouple of flare as illus- 2.3. Experimental analysis
trated in Fig. 1. The length and inner diameter of stainless steel
reactor were 540 mm and 140 mm, respectively. Sewage sludge was obtained from the Pasakoy Advanced Bio-
Instant temperature of heater cabin, gas pipe and flare were logical Wastewater Treatment Plant (WWTP) in Istanbul. While
measured with thermocouples. The reactor was completely auto- the Pasakoy WWTP was designed in an A2O process scheme
mated to obtain the instant temperatures at the three locations (Sözen et al., 2009), it is operated at an extended aeration mode
mentioned. The reactor was operated at a batch mode. In a typical at a high sludge age of 30 days. This way, the biomass is mineral-
run, the temperature of the electrical heating furnace was ized within the system at the expense of additional volume and
increased at a heating rate of approximately 10 °C/min up to the aeration (Insel et al., 2015). The biological sludge sampled for the
desired pyrolysis temperature. After the temperature was stabi- study, leaves the system with an initial dry matter (DM) content
lized in the furnace, the stainless steel reactor with the sludge sam- of 1.3% and sequentially processed in a dewatering and a drying
ple was placed into the furnace carefully. The residence time of the unit, increasing its DM content to 30% and 94% respectively. Conse-
experiment took approximately 1–2 h depending on the experi- quently, this study was carried out using an aerobically stabilized
mental conditions, i.e. temperature and rotation speed. The syngas and dried sludge with a DM content of 94%. A picture of the sample
evolved during the experiments was observed for 40–60 min at of dried sludge used in the study was provided in the supplemen-
each run conducted at specified operating conditions. The temper- tary materials.
ature was monitored automatically and the pressure of the gas was Dried sludge was subjected to a series of proximate, elemental
also observed from the manometer located on the pipe. and calorific value analyses. The proximate analysis was conducted
The syngas was collected at the outlet 4 and the composition to determine volatile matter; ash; fixed carbon and the total sulfur
was determined by means of a portable MRU-VarioPlus gas ana- content of the representative sludge sample using LECO TGA701
lyzer (Deutschland). Evolved gas was then passed through the (USA) standard equipment in compliance with ASTM D3172
pipes and was disposed with flare. The tar was flushed from outlet (ASTM D3172, 2013). All analyses required a re-drying process at
5 (Fig. 1). The yields and composition of the principal products 105 °C to completely evaporate the initial moisture content of 6%
depended on operational conditions of the pyrolysis process. Pyrol- of the sludge sample.
ysis temperature and rotational speed were chosen as the repre- The sample was then subjected to elemental analysis for the
sentative parameters to determine the effect of operational assessment of carbon, hydrogen, and nitrogen with LECO
conditions on principle products. After each run, the amounts of TruSpec-CHN (USA) along with sulphur with TruSpec-S elemental
tar and biochar were weighted and the amount of the syngas analyzer (USA) using the methodology defined in ASTM D5373
was calculated by the weight difference given in Eq. (1). MS is and ASTM D4239, respectively (ASTM D5373, 2014; ASTM
the mass of syngas (g); MSS is the mass of sewage sludge fed into D4239, 2014). Oxygen was also calculated from the equation given
the reactor (g); MT is the mass of tar (g) and MB is the mass of bio- in the ASTM D5373 (ASTM D5373, 2016).
char (g). Higher Heating Value (HHV) and Lower Heating Values (LHV) of
sewage sludge, tar, and biochar were determined by using LECO
M S ¼ M SS  ðMT þ MB Þ ð1Þ
AC-600 bomb calorimeter (USA) in compliance with the methodol-
The experiments were conducted on eight different runs (Run ogy given in ASTM-D-5865 (ASTM D5865, 2013). The higher heat-
1-Run 8) at three different temperatures (450 °C, 600 °C, and ing value was measured at dry sample whereas the lower heating
850 °C) at a rotation speed of 10 Hz, 40 Hz and 60 Hz. The mass value was measured at original sample at 6% moisture content. All
of sludge was kept around 500–555 g at each run as indicated in the analytical equipments were in full-working order. They have
Table 1. Energy and mass balance were established based on only been previously tested for operability.

Fig. 1. Schematic illustration of the experimental set-up.

220 C. Karaca et al. / Waste Management 78 (2018) 217–226

Table 1
Operating conditions of the experiments.

Experiments Temperature (¯C) Rotation Speed (Hz) Sludge (Mss)

Total Organic*
gr gr
Run 1 450 60 555 358
Run 2 600 10 555 358
Run 3 600 40 520 335
Run 4 600 60 510 330
Run 5 850 10 550 355
Run 6 850 40 1030 665
Run 7 850 60 500 325
Run 8 850 60 555 358
*
65% organic matter in the sludge.

The syngas was analyzed with a MRU VarioPlus portable gas and elemental analysis on ash-free basis. The elemental analyses
chromatography. Gas chromatography was used to measure the showed that the organic fraction of the sludge approximately con-
gas composition of evolved syngas examining the weight percent- sisted of 34% C, 4% H, 5% N and 20% O, leading to a higher heating
age of CO, CO2, N2, CH4, and H2. The specific calorific values of each value of 14.435 kJ and a lower heating value of 13.535 kJ per kg dry
gas components (CH4: 35.648 kJ/m3, H2: 10.732 kJ/m3, CO: 12.552 matter (DM). The calorific value of the sludge 13.535 kJ/kg DM,
kJ/m3) were taken into account together with the weight percent- when calculated in terms of volatile suspended solids (VSS) that
age of gas composition in order to calculate the calorific value of usually defines the organic fraction of biomass corresponded to
the syngas. The volume of evolved syngas was calculated using 20.815 kJ/kg VSS. Adopting the COD equivalence of 1 kg COD/
the known specific gravity of each gas components in the syngas 0.75 kg VSS suggested in the ASM3 model (Koch et al., 2000), the
(CH4: 0.7 kg/m3, H2: 0.09 kg/m3, CO: 1.2 kg/m3, CO2: 1.9 kg/m3, calorific value of sludge may also be expressed as 15.610 kJ/kg bio-
N2: 1.2 kg/m3, O2: 1.38 kg/m3). mass COD, a value compatible with previously reported levels in
the literature.
The results of elemental analyses of sludge from two different
3. Results and discussion
treatment plants (Orhon and Artan, 1994) were compared. It
should be noted that the carbon content of the biomass used in this
3.1. Sludge characterization
study (34%) is significantly lower than that of the other sludge
compositions (Prague; 51% and Sedlec; 50%) given in supplemen-
The Pasakoy treatment plant, which supplied the biological
tary material Table A, due to internal mineralization and conver-
sludge sample for the study, currently treats a municipal sewage
sion to CO2 in the extended aeration mode of plant operation.
flow of around 130.000 m3/d with an average COD content of
The results also enabled to derive an empirical formula for the
535 mg/L (Sözen et al., 2009), a level compatible with sewage char-
sludge as C7H11NO3. This formula does not contain P and S, because
acteristics previously assessed in Istanbul Metropolitan Area (Orhon
it is expressed as simple as possible; mainly to compare with the
et al., 1994; Tas et al., 2009) aside from COD, it contains slightly
historical elementary composition of activated sludge defined by
higher levels of 61 mg/L of total nitrogen and 11 mg/L of total
the C5H7NO2 formula extensively used in process stoichiometry
phosphorus.
(Orhon, 2015; Porges et al., 1956).
Results of the characterization experiments are outlined in
The results may be compared with several pyrolysis studies that
Table 2; they indicated that the dry solids content of sludge
were carried out at high temperature under different experimental
included a high inorganic (ash) fraction of 35%, presumably reflect-
conditions, where the ash content differed in a range of 30–52.6%
ing accumulation of inorganic material in biomass, due to extended
depending on the origin of the sewage sludge, and the high calori-
aeration mode of plant operation at a sludge age of 30 d. It should
fic values ranged between 13.941 and 24.292 kJ/kg DM sewage
be noted that the proximate analysis were carried out on dry basis
sludge (Fonts et al., 2009; Pedroza et al., 2014; Ospanov et al.,
Table 2
2015; Inguanzo et al., 2002).
The characteristics of the dried sludge.

Parameter Characteristics
3.2. Mass balance for organic matter
Proximate Analyses (wt%)
Moisture (%) 6.0*
Pyrolysis experiments were conducted with the main objective
Volatile Matter (%) 55.5
Fixed Carbon (%) 9.0 of identifying the optimum operating conditions that would max-
Ash (%) 35.5 imize energy recovery, preferably in terms of syngas production; as
Total Sulfur (%) 0.98 mentioned before, syngas can be an easy and suitable substitute
Elemental Analyses (wt%) for natural gas, which is widely used in treatment plants and
Carbon (C) 34.08 industrial activities for various purposes. Assessment of experi-
Hydrogen (H) 4.33
mental results was conducted in two consecutive steps: Distribu-
Nitrogen (N) 5.34
Sulphur (S) 0.98
tion of (i) organic matter and (ii) energy among the principal end
Oxygen (O)** 19.69 products in eight different runs designed to reflect the effect of
Heating Values (kJ/kg)
the two selected operating parameters, pyrolysis temperature
Higher Heating Value*** 14.435 and rotation speed. The results of the organic matter distribution
Lower Heating Value* 13.535 under different operating conditions are outlined in Figs. 2 and 3.
*
Original sample.
As previously mentioned, the volatile matter (organic) and ash
**
Calculated from the difference. (inorganic) contents of sludge were determined as 65 wt% and
***
Dry sample. 35 wt%, respectively. It was clear that tar and syngas originated
 C. Karaca et al. / Waste Management 78 (2018) 217–226 221

50 45 40 43

Organic matter
35

content (%)
40
Biochar
30 20 17 Tar
20
10 Syngas
0
600 850
Run 2 Run 5
Temperature (°C )
(a)
70 61 58
Organic matter

60 52
content (%)

50 41 38 Biochar
36
40 29
30 21 24 Tar
20 15 12 13 Syngas
10
0
450 600 850 850
Run 1 Run 4 Run 7 Run 8
Temperature (°C)
(b)
Fig. 2. Organic matter (a) Yields of biochar, tar and syngas products with different temperatures at the rotation speed of 10 Hz (b) Yields of biochar, tar and syngas products
with different temperatures at the rotation speed of 60 Hz.

from organic portion of sewage sludge and the biochar contained measurements of the volume and composition of the generated
the whole inorganic part (35 wt%) of the sludge together with a syngas. The energy balance was set by first measuring the calorific
portion of organic matter that could not been destructed via pyrol- values of sludge, tar and biochar and then, by accounting for the
ysis process. In accordance with the objective of the study, the remaining part of the energy input as the energy encapsulated in
experiments were focused to maximize the syngas production, the syngas. The original calorific value (kJ/kg) of sludge, tar, biochar
and to lower to the possible extent of tar and biochar. and syngas were given in supplementary material Table B. The dis-
These figures provide a graphical explanation of the results as tribution of energy among the principal end products for each run
outlined below: For the biochar, pyrolysis at 850 °C with rotation is outlined in Table 3. Using the mass, the volume and the compo-
speeds of 40 and 60 Hz, kept the organic matter fraction (OMF) sition of the syngas, the calorific value (CV) of syngas obtained in
at the minimum level of 12–13%. When the rotation speed was each run under different operating conditions was calculated as
reduced to 10 Hz, the OMF was increased to 17%. Experiments con- shown in Table 3.
ducted at 600 °C indicated incomplete organic matter reduction as The energy conservation and recovery potential of pyrolysis
they yielded a higher level of OMF of 15–17%, regardless of the based on experimental results for Run 8, which represents best
selected rotation speed. The OMF corresponding to 400 °C was operating conditions, i.e. at 850 °C with a rotation speed of 60
even higher as 21% at 60 Hz. For the tar, the OMF was measured Hz. The effect of operating conditions on the energy balance of
in the range of 28–36% in pyrolysis experiments conducted at the system is evaluated in Table 4.
850 °C with rotation speeds of 40 and 60 Hz. Reducing the rotation The data displayed in Table 4 showed that when the pyrolysis
speed to 10 Hz, increased the OMF to 40%. At 600 °C, a 6% increase system was adjusted to best operating conditions at high temper-
was recorded for the corresponding OMF, which remained in the ature and high rotation speed, around 74% of the energy in sludge
range of 34–40% at rotation speeds of 40 and 60 Hz. Dropping could potentially be recovered as syngas and tar. It should be noted
the rotation speed to 10 Hz at the same temperature maximized that the experiments were conducted in a batch system. In contin-
OMF to 45%. Pyrolysis at 450 °C also yielded a high OMF of 41% uous systems, the syngas generation could be significantly
even at 60 Hz. For the syngas, the OMF basically remained at the increased by full recovery of condensable gaseous components,
same range of 52–61% in pyrolysis experiments conducted at i.e. avoiding partial condensation into tar under batch operation,
850 °C and 600 °C at rotation speeds at 40 Hz and above. Dropping and recycling tar back to the reactor for allowing maximum transi-
the rotation speed to 10 Hz decreased the OMF by 9–17% at 850 °C tion into the gaseous phase.
and 13–16% at 600 °C. Pyrolysis at 450 °C, was quite ineffective
since the OMF remained at 38% at the rotation speed of 60 Hz. In 3.4. Evaluation of results
short, run 8; at 850 °C and 60 Hz, provided the optimum conditions
to maximize OMF for the syngas at the range of 52–61%, and kept The study basically investigated high temperature pyrolysis for
the OMF at the minimum level of 12–13% for the biochar. the purpose of exploring its performance and potential of energy
recovery preferably as gaseous products (syngas). Important
3.3. Mass balance for energy recovery aspects on the effect of pyrolysis temperature and rotation speed
are displayed in Figs. 2 and 3. First, rotation speed of 10 Hz was
As previously mentioned, energy mass balance was established not suitable for this purpose, since it increased the energy content
based on the results of four runs (Run 1, 4, 5, 8) conducted with of biochar; similarly, the energy recovered as tar was increased to
222 C. Karaca et al. / Waste Management 78 (2018) 217–226

Organic matter content

70 58 61
60
50 45
40 35
30 Biochar
(%)
30 20 24
20 12 15 Tar
10 Syngas
0
10 Hz 40 Hz 60 Hz
Run 2 Run 3 Run 4
Rotation Speed (Hz)
(a)
Organic matter content

70 60 58
60
50 40 43
40 29
28
(%)

30 Biochar
17 13
20 12
10 Tar
0 Syngas
10 Hz 40 Hz 60 Hz
Run 5 Run 6 Run 7
Rotation Speed (Hz)
(b)
Fig. 3. Organic matter (a) Yields of biochar, tar and syngas products with different rotation speeds at 600 °C (b) Yields of biochar, tar and syngas products with different
rotation speeds at 850 °C.

Table 3
Components and calorific values of syngas under different operating conditions.

Runs Temperature (°C) Rotation Speed (Hz) Calorific Value Syngas Volume Gas Components Syngas CV (kJ/m3)
(volume basis)
Sludge Biochar Tar Syngas Volume CH4 H2 CO CO2
kJ kJ kJ kJ (m3) (%) (%) (%) (%)
Run 1 450 60 7510 2720 1828 2406 0.17 41 35 11 13 19.598
Run 4 600 60 6904 2046 971 3423 0.22 34 33 20 13 18.054
Run 5 850 10 7443 2335 2138 2623 0.19 28 37 20 15 16.297
Run 8 850 60 7510 2029 1933 3535 0.24 34 35 13 18 17.422

Table 4
Energy balance of pyrolysis experiments under different operating conditions.

Experiments Temperature Rotation Speed Sludge Biochar Tar Syngas Possible Error
(°C) (Hz) (kJ) (kJ) % (kJ) % (kJ) % %
Run 1 450 60 7510 2720 36 1828 24 2406 35 6
Run 4 600 60 6904 2046 32 971 27 3423 33 7
Run 5 850 10 7448 2335 31 2138 29 2628 35 5
Run 8 850 60 7510 2029 26 1933 26 3540 48 <1

the same or higher level than that of syngas, regardless of temper- The merit of exploring best operating conditions to optimize
ature (Fig. 2). Second, high rotation speed of pyrolysis at 600 °C energy recovery can best be summarized with the data given in
lowered the energy of tar in favor of syngas (Fig. 3a). Finally, high the supplementary material Table C. In the literature, the ratio of
rate pyrolysis at 850 °C yielded the best energy distribution among organic content in the sludge that remained after pyrolysis was
end products, maximizing syngas generation both at rotation reported in the range of 17–35% (Zhang et al., 2011; Pedroza
speeds of 40 and 60 Hz (Fig. 3b). It should be mentioned again that et al., 2014; Inguanzo et al., 2002; Hossain et al., 2009). The organic
in continuous pyrolysis systems, recovering condensable gaseous content of biochar under optimum operating conditions in this
products and/or recycling tar back into the pyrolysis unit could study was calculated 12%, significantly lower than the reported
substantially increase the syngas generation. range, although the organic content of sludge was practically the
 C. Karaca et al. / Waste Management 78 (2018) 217–226 223

same. The difference was simply due to the fact that the operating As briefly mentioned above, the highlights displayed in the
conditions in other studies were randomly selected, without any Table 6, do not offer a platform for benchmarking, mainly because
concern to minimize the organic content of biochar. they only concentrate on a selected sludge type, with no informa-
Comparison of the organic content and the corresponding tion on the origin, the magnitude and the mode of treatment that
energy in biochar also revealed an interesting feature of pyrolysis generated it. They give access only to the visible part, i.e. what frac-
performance. As the energy and COD contents are theoretically tion of energy can be recovered from sludge, but no access for
equivalent, Table 5 shows that the COD/organic matter ratio behind the scene information, i.e. what fraction of the energy con-
(COD/VSS) increased from 1.7 g COD/g VSS at 450 °C to around tained in the wastewater is consumed and wasted before generat-
1.82–2.16 g COD/g VSS at 850 °C. At this point, it should be remem- ing the sludge used in the studies.
bered that the dried sludge used in the study could be character- Undoubtedly, the energy recovery management requires a com-
ized by an empirical formula C7H11NO3, which reflects a COD/VSS prehensive/unified approach in a life cycle assessment mode, neces-
ratio of 1.53 g COD/g VSS. With reference to this ratio, it could be sarily covering all the essential parameters related to the design
deduced that the organic content of biochar was almost the same and operation of the treatment plant, because this is how the
as that of sludge itself at 450 °C, whereas it became gradually energy is best conserved even before the sludge is generated.
reduced to approach elemental carbon as the temperature
increased. Since carbon black (elemental carbon) is the carbon form 3.5. Practical implications
with a COD/VSS ratio of 2.6 g COD/g VSS, biochar still contains a
slight portion of unreduced organic impurities even at 850 °C. On The results of the study provides strong indications that high
the other hand, the COD/VSS ratio of 1.53 g COD/g VSS associated temperature pyrolysis may be considered as an alternative to
with the sludge is slightly higher than 1.42 g COD/g VSS defined anaerobic digestion in the conventional wastewater treatment
by the historical C5H7NO2 formula or 1.33 g COD/g VSS suggested scheme, as a more efficient energy recovery process from sludge.
by ASM3 (Çokgör et al., 1998; Koch et al., 2000). The observed dif- At this stage, it would be instructive to carry out a preliminary
ference could be presumably explained by a higher content of analysis comparing the net energy recovery potentials of the two
residual microbial products, due to plant operation at excessively systems. The biogas generated in the anaerobic digestion may be
high sludge age of 30 d. estimated using the range of 35–50% for VSS and/or COD destruc-
This evaluation should also underline that similar studies tion as suggested in the literature (Bolzonella et al., 2012; Svaldal
reported in the literature commonly adopted the characteristics and Kroiss, 2011; Gebreeyessus and Jenicek, 2016). The sludge
and the calorific value of the sludge studied as the starting point used in the pyrolysis experiments (550 g) was characterized by a
of their appraisals: They overlooked the energy conservation volatile suspended solids ratio of 65 wt%; this ratio implies that
achieved in the treatment plant through the generated sludge. under the same conditions, the sample would introduce 350 g of
Obviously, a unified basis of estimation can only be obtained if organic sludge into anaerobic digestion. Adopting an average ratio
energy recovery is considered as an integral part of energy conser- of 40% for VSS and/or COD, for the destruction in anaerobic diges-
vation. In simpler terms, wastewater sludge should not be consid- tion, the resulting magnitude of organic matter biodegradation
ered alone, without consideration of key parameters that define may be calculated as 140 g VSS.
the type of treatment. They can be qualified at best ‘‘as random Using the characteristic of the sludge in the study (1.53 g COD/g
research efforts, lacking the basic information for a unified evalua- VSS), this amount also corresponds to 215 g COD of biodegraded
tion”. As a basis for reference, Table 6 lists the highlights of four dif- organic matter. Under mesophilic conditions, anaerobic biodegra-
ferent studies conducted on the sludge sourced by different dation of 215 g sludge COD approximately generates 0.075 m3
wastewater treatment plants (WWTP), together with similar methane during anaerobic digestion (1 g COD = 0.35 L CH4). The
results obtained in this study. energy potential of 0.075 m3 methane corresponds to 2677 kJ
It should be noted from Table 6 that the sewage sludge with a (1 m3 CH4  35.648 kJ) (Metcalf and Eddy, 2003). From values
high heating value of 14.435 kJ/kg as indicated run 8 in this study, given above, the energy potential of anaerobic digestion can be
conducted at 850 °C and 60 Hz, yielded an energy recovery of 74% theoretically approximated as 7657 kJ/kg VSS.
presenting an energy potential of 15.506 kJ per kg organic sludge. The experimental results in this study determined an energy
A general inspection of related data also included in Table 6 potential of the syngas as 15.606 kJ per kg organic sludge, in high
revealed that (i) Ospanov et al., 2015 recovered 71% energy on temperature pyrolysis corresponding to 74% energy recovery. A
the basis of tar and syngas, similar to this study, as they were preliminary analysis comparing this potential with 7657 kJ/kg
carried out under the same conditions as 850 °C and 50 Hz. VSS related to anaerobic digestion shows the energy recovery
However, Ospanov et al., 2015 used sludge with a calorific value potential of high temperature pyrolysis as more than twice higher
of 21.234 kJ/kg that displayed a totally different character resulting than the conventional anaerobic digestion. It should be further
in the recovery of 23.095 kJ per kg organic sludge. (ii) Pedroza noted that pyrolysis achieved thermo-destruction of almost all
et al., 2014 reported the recovery of 40% energy as total syngas available organic matter in sludge. In full-scale applications, a
and tar much lower than the results of other studies in the slight portion of the generated energy remains with the biochar,
literature, presumably due to the lower volatile matter and higher as organic carbon. The remaining part is recovered mostly as syn-
ash content of the sludge analyzed. gas. However, 10–15% of the syngas recovered is recirculated back

Table 5
The COD/VSS ratio of biochar under different operating conditions.

Experiments Temperature Rotation Speed (Hz) Organic Calorific Value COD/VSS

(°C)
gr % kJ %
Run 1 450 60 75 21 2720 36 1.70
Run 4 600 60 48 15 2046 32 2.13
Run 5 850 10 60 17 2335 31 1.90
Run 8 850 60 43 12 2029 26 2.16
224 C. Karaca et al. / Waste Management 78 (2018) 217–226

Table 6
Highlights of high temperature pyrolysis.

Parameters Inguanzo et al. (2002) Ospanov et al. (2015) Pedroza et al. (2014) Dominguez (2006) This Study
Characteristics of the WWTP
Wastewater COD (mg/L) NA* NA NA NA 535
Sludge age (d) NA NA NA NA 30
Sludge source Anaerobically digested Secondary Settling Tank Aerobically digested Aerobically digested Anaerobically digested
Sludge HHV (kJ/kg) 16.527 21.234 21.087 16.694 14.435
Sludge Characteristics
Moisture % 5.2 5.3 6 71 6
Ash % 29.5 30 38 31 35
Volatile matter % 60.7 65 54 62 55
Carbon % 35 47.7 28 52 34
Operational Conditions
Temperature (°C) 850 850 650 1040 850
Heating Rate (°C min1) 60 50 NA NA 60
Rotation Speed (Hz) NA NA 30 NA 60
Total product yields
Gas % 17 17 24 30 34
Solid % 45 42 52 10 42
Liquid % 40 41 24 57 23
Energy
Gas % 22 17 20 28 48
Solid % 12 24 14 4 29
Liquid % 63 54 20 5 26
Energy Recovery** (%) 85 71 40 33 74
kJ/kg organic sludge 23.313 23.096 15.480 11.297 15.606
*
NA: not available.
**
Calculated based on tar and syngas.

to meet internal energy requirements and maintain the reactor at sewage flow of 130.000 m3/d, with an influent COD of 0.535 kg/
the desired temperature (Cao and Pawlowski, 2012). Accounting m3. Although it is a nutrient removal plant, it is unfortunately
for the internal energy requirements of pyrolysis the net energy operated at the extended aeration mode, at a sludge age of 30 d.
generation may be reduced to around 13.700 kJ/kg organic sludge. The total COD load of the treatment is around 70.000 kg/d. The
This still represents a significant edge compared to anaerobic selected mode of system operation generates 15.000 kg/d of sludge
digestion and definitely gives a promising perspective for a wider so that the conserved sludge ratio remains only as 21% both in
comparison, which is not given in the preliminary calculations pro- terms of influent COD and energy. The calculation details are pro-
vided here. Furthermore, anaerobic digestion leaves behind the vided in the supplementary material section. This study indicated
major fraction of sludge with 2–3% dry matter content; it also that around 70% of the sludge energy is recoverable with high rate
involves substantial costs for dewatering and final disposal of pyrolysis. This way, the overall magnitude of energy recovery
residual sludge. becomes limited to 14% regardless of how efficient is the high tem-
It may be argued that pyrolysis requires a preliminary drying perature pyrolysis for recovering energy from sludge. Based on the
step that would reduce the moisture content of the sludge to less calorific value of 14.226 kJ/kg COD, this corresponds to the recov-
than 20%, a process requiring energy. However, this energy con- ered energy of 15.107 kJ/d or the equivalent of 4200 m3 of natural
sumption should not be directly associated with pyrolysis, because gas per day.
it should be envisaged as the necessary component of the final If the operation of the treatment plant was to be changed and
sludge disposal process, i.e. incineration, land disposal, etc., More- adjusted to a sludge age of 10 d, like all routine nutrient removal
over, pyrolysis also secures substantial sludge reduction for final plants (Insel et al., 2015), the recovery of influent COD into sludge
disposal, leaving only behind the biochar, a commercially valuable would increase to 32%. This means that pyrolysis would recover a
by-product (Samolada and Zabaniotou, 2014). It is surprising to much higher energy level of 22.107 kJ/d, corresponding to 6400 m3
note that in all the evaluations towards energy efficient treatment of natural gas per day. The evaluations exemplified above indicate
systems, anaerobic digestion/biogas maintains its place as the sole the need to give serious consideration to novel biological treat-
energy source. However, this study clearly identified high temper- ment technologies for organic carbon removal, using membrane
ature pyrolysis as a much more promising alternative for this pur- bioreactors instead of traditional gravity settling, operated at
pose. This should be underlined as the essential motivation for the extremely high rates in a sludge age range of 0.5–2.0 d. Related
evaluations in this study. studies reported that these systems called as super-fast membrane
At this stage, it should be remembered that the energy recovery bioreactors (SFMBR) possess the potential of increasing the conser-
from wastewater requires a unified management sequence involv- vation ratio of influent COD into sludge to above 70% (Sözen et al.,
ing to maximize (i) energy conservation in sludge by adopting high 2016; Sözen et al., 2017).
rate activated sludge systems (ii) energy recovery from sludge
implementing a more efficient process compared to anaerobic
digestion. In this context, the sludge sample used in this study rep- 4. Conclusion
resented ‘‘a worst-case scenario in terms of energy conservation”,
since it was aerobically stabilized within the treatment system. As Under optimum operating conditions at 850 °C and rotation
a support of the unified approach mentioned above, this statement speed of 60 Hz, high temperature pyrolysis proved to be an effec-
should be further clarified using the data of the treatment plant tive novel technology, which displayed an energy recovery poten-
where the sludge was taken: As summarized in the materials and tial of 74% as syngas and tar. A preliminary evaluation of the
methods section, the Pasakoy activated sludge plant treats a experimental data indicated that high temperature pyrolysis could
 C. Karaca et al. / Waste Management 78 (2018) 217–226 225

potentially recover more than twice as much energy as compared Heidrich, E.S., Curtis, T.P., Dolfing, J., 2011. Determination of the internal chemical
energy of wastewater. Environ. Sci. Technol. 45, 827–832.
to anaerobic digestion. The results clearly showed that high tem-
Horn, A.L., Düring, R.A., Gäth, S., 2003. Comparison of decision support systems for
perature pyrolysis embodied all the necessary attributes to replace an optimised application of compost and sewage sludge on agricultural land
the traditional anaerobic digestion, both in terms of energy recov- based on heavy metal accumulation in soil. Sci. Total Environ. 311, 35–48.
ery and disposal of end products. Hospido, A., Carballa, M., Moreira, M., Omil, F., Lema, J.M., Feijoo, G., 2010.
Environmental assessment of anaerobically digested sludge reuse in
Energy conservation in sludge should be regarded as an integral agriculture: potential impacts of emerging micropollutants. Water Res. 44,
component of energy recovery management. The energy conserva- 3225–3233.
tion component requires a major change in the conventional treat- Hossain, M.K., Strezov, V., Nelson, P.F., 2009. Thermal characteristics of the products
of wastewater sludge pyrolysis. J. Anal. Appl. Pyrol. 85, 442–446.
ment strategy towards high rate systems and higher rates of sludge Inguanzo, M., Domınguez, A., Menéndez, J.A., Blanco, C.G., Pis, J.J., 2002. On the
generation. The adopted strategy should equally consider and eval- pyrolysis of sewage sludge: the influence of pyrolysis conditions on solid, liquid
uate the energy in sludge as a fraction of the energy contained in and gas fractions. J. Anal. Appl. Pyrol. 63, 209–222.
Insel, G., Cokgor, E., Tas, D.O., Sozen, S., Orhon, D., 2015. Impact of the anoxic volume
the wastewater so that the adopted management scheme could ratio on the dynamics of biological nitrogen removal under extended aeration
cover all the essential parameters of the treatment plant, because conditions. Water Air Soil Pollut. 226, 1.
this is how the energy is best conserved even before the sludge Karaca, C., Okutan, H.C., Sozen, S., Orhon, D., 2015. Energy recovery with syngas
production from sewage sludge using high rate pyrolysis at high temperature.
is generated. Proc. SEEP 2015, 11–14.
Koch, G., Kuhni, M., Gujer, W., Siegrist, H., 2000. Calibration and validation of
activated sludge model No. 3 for Swiss municipal wastewater. Water Res. 34,
Appendix A. Supplementary material 3580–3590.
Lederer, J., Rechberger, H., 2010. Comparative goal-oriented assessment of
conventional and alternative sewage sludge treatment options. Waste
Supplementary data associated with this article can be found, in
Manage. 30, 1043–1056.
the online version, at https://doi.org/10.1016/j.wasman.2018.05. Liu, X., Chang, F., Wang, C., Jin, Z., Wu, J., Zuo, J., Wang, K., 2018. Pyrolysis and
034. subsequent direct combustion of pyrolytic gases for sewage sludge treatment in
China. Appl. Therm. Eng. 128, 464–470.
Luque, R., Menéndez, J.A., Arenillas, A., Cot, J., 2012. Microwave-assisted pyrolysis of
References biomass feedstocks: the way forward? Energy Environ. Sci. 5, 5481–5488.
McCarty, P.L., Bae, J., Kim, J., 2011. Domestic wastewater treatment as a net energy
producer-Can this be achieved? Environ. Sci. Technol. 45, 7100–7106.
Antoniou, N., Zabaniotou, A., 2013. Features of an efficient and environmentally
Metcalf, E., Eddy, P., 2003. Wastewater Engineering: Treatment and Reuse, Boston,
attractive used tyres pyrolysis with energy and material recovery. Renew. Sust.
McGraw-Hill.
Energy Rev. 20, 539–558.
Miandad, R., Barakat, M.A., Aburiazaiza, A.S., Rehan, M., Nizami, A.S., 2016a.
ASTM D3172-13, 2013. Standard Practice for Proximate Analysis of Coal and Coke,
Catalytic pyrolysis of plastic waste: a review. Process Saf. Environ. Prot. 102,
ASTM International, West Conshohocken, PA, <www.astm.org>.
822–838.
ASTM D5865-13, 2013. Standard Test Method for Gross Calorific Value of Coal and
Miandad, R., Nizami, A.S., Rehan, M., Barakat, M.A., Khan, M.I., Mustafa, A., Ismail, I.
Coke, ASTM International, West Conshohocken, PA, <www.astm.org>.
M.I., Murphy, J.D., 2016b. Influence of temperature and reaction time on the
ASTM D5373-16, 2016. Standard Test Methods for Determination of Carbon,
conversion of polystyrene waste to pyrolysis liquid oil. Waste Manage. 58, 250–
Hydrogen and Nitrogen in Analysis Samples of Coal and Carbon in Analysis
259.
Samples of Coal and Coke, ASTM International, West Conshohocken, PA, <www.
Miandad, R., Barakat, M.A., Rehan, M., Aburiazaiza, A.S., Ismail, I.M.I., Nizami, A.S.,
astm.org>.
2017a. Plastic waste to liquid oil through catalytic pyrolysis using natural and
ASTM D4239-14e2, 2014. Standard Test Method for Sulfur in the Analysis Sample of
synthetic zeolite catalysts. Waste Manage. 69, 66–78.
Coal and Coke Using High-Temperature Tube Furnace Combustion, ASTM
Miandad, R., Barakat, M.A., Aburiazaiza, A.S., Rehan, M., Ismail, I.M.I., Nizami, A.S.,
International, West Conshohocken, PA, <www.astm.org>.
2017b. Effect of plastic waste types on pyrolysis liquid oil. Int. Biodeterior
Basßaran, S.T., Aysel, M., Kurt, H., Ergal, I., Kumru, M., Akarsubasßı, A., Sözen, S., Orhon,
Biodegradation 119, 239–252.
D., 2012. Removal of readily biodegradable substrate in super fast membrane
Novak, J.T., Verma, N., Muller, C.D., 2007. The role of iron and aluminum in digestion
bioreactor. J. Membr. Sci. 423, 477–486.
and odor formation. Water Sci. Technol. 56, 59–65.
Basu, P., 2010. Biomass Gasification and Pyrolysis: Practical Design and Theory.
Øegaard, H., 2004. Sludge minimization technologies – an overview. Water Sci.
Academic press, Oxford, UK.
Technol. 49, 31–40.
Bolzonella, D., Fatone, F., Di Fabio, S., Cecchi, F., 2012. A high rate mesophilic,
Orhon, D., Artan, N., 1994. Modelling of Activated Sludge Systems. Technomic
thermophilic and temperature phased anaerobic digestion of waste activated
Publishing Co. Inc, Lancaster, PA.
sludge: a pilot study. Waste Manage. 32, 1196–1201.
Orhon, D., Sözen, S., Ubay, E., 1994. Assessment of nitrification-denitrification
Bushwell, A.M., 1957. Fundamentals of anaerobic treatment of organic wastes.
potential of Istanbul domestic wastewaters. Water Sci. Technol. 30, 21–30.
Sewage Ind. Wastes 29, 717–721.
Orhon, D., 2015. Evolution of the activated sludge process: the first 50 years. J.
Cao, Y., Pawłowski, A., 2012. Sewage sludge-to-energy approaches based on
Chem. Technol. Biot. 90, 608–640.
anaerobic digestion and pyrolysis: brief overview and energy efficiency
Ospanov, K., Myrzahmetov, M., Zapparov, M., 2015. Study of the products of
assessment. Renew. Sust. Energy Rev. 16, 1657–1665.
pyrolysis recycling: sewage sludge in the aeration station Almaty, Kazakhstan.
Chon, D.H., Rome, M., Kim, Y.M., Park, K.Y., Park, C., 2011. Investigation of the sludge
Proc. Eng. 117, 288–295.
reduction mechanism in the anaerobic side-stream reactor process using
Pedroza, M.M., Sousa, J.F., Vieira, G.E.G., Bezerra, M.B.D., 2014. Characterization of
several control biological wastewater treatment processes. Water Res. 45,
the products from the pyrolysis of sewage sludge in 1 kg/h rotating cylinder
6021–6029.
reactor. J. Anal. Appl. Pyrol. 105, 108–115.
Çokgör, E.U., Sözen, S., Orhon, D., Henze, M., 1998. Respirometric analysis of
Piskorz, J., Scott, D., Westerberg, I., 1986. Flash pyrolysis of sewage sludge. Ind. Eng.
activated sludge behaviour—I. Assessment of the readily biodegradable
Chem. 25, 265–270.
substrate. Water Res. 32, 461–475.
Porges, N., Jasewicz, L., Hoower, S.R., 1956. Principles of Biological Oxidation, in
Domínguez, A., Menéndez, J.A., Inguanzo, M.L., Pis, J.J., 2005. Investigations into the
Biological Treatment of Sewage and Industrial Wastes: Vol. 1, Aerobic
characteristics of oils produced from microwave pyrolysis of sewage sludge.
Oxidation. Reinhold Publishing Co, New York.
Fuel Process Technol. 86, 1007–1020.
Samolada, M.C., Zabaniotou, A.A., 2014. Comparative assessment of municipal
Dominguez, A., 2006. Production of bio-fuels by high temperature pyrolysis of
sewage sludge incineration, gasification and pyrolysis for a sustainable sludge-
sewage sludge using conventional and microwave heating. Bioresource
to-energy management in Greece. Waste Manage. 34, 411–420.
Technol. 97, 1185–1193.
Scott, D.S., Piskorz, J., Radlein, D., 1985. Liquid products from the continuous flash
Dominguez, A., Fernandez, Y., Fidalgo, B., Pis, J.J., Menendez, J.A., 2008. Bio-syngas
pyrolysis of biomass. Ind. Eng. Chem. 24, 581–588.
production with low concentration of CO2 and CH4 from microwave-induced _
Sözen, S., Orhon, D., Çokgor, E. U., Insel, G., Karahan, Ö., Yağcı, N., Dogruel, S., Zengin
pyrolysis of wet and dried sewage sludge. Chemosphere 70, 397–403.
Balcı, G., Ölmez Hancı, T., Okutman Tasß, D., Dülekgürgen, E., Çığgın, A., Pala, I.,
Council, European, 1999. Council Directive 99/31/EC on the landfill of waste. Official _
Katipoğlu, T., 2009. Ileri biyolojik atıksu arıtma tesislerinde model bazlı proses
J. Eur. Commun. L182, 0001–19.
optimizasyonu. ItüDergisi/e.19, pp. 1–2.
Fonts, I., Azuara, M., Geo, G., Munillo, M.B., 2009. Study of pyrolysis liquids obtained
Sözen, S., Cokgor, E.U., Insel, G., Tas, D.O., Dulkadiroglu, H., Karaca, C., Filibeli, A.,
from different sewage sludge. J. Anal. Appl. Pyrol. 85, 184–191.
Meric, S., Orhon, D., 2015. Scientific basis of dissolved organic carbon limitation
Fytili, D., Zabaniotou, A., 2008. Utilization of sewage sludge in EU application of old
for landfilling of municipal treatment sludge – is it attainable and justifiable?
and new methods—a review. Renew. Sust. Energy Rev. 12, 116–140.
Waste Manage. 34, 1657–1666.
Garrido, J.M., Fdz-Polanco, M., Fdz-Polanco, F., 2013. Working with energy and mass
Sözen, S., Basßaran, S.T., Akarsubasßı, A., Ergal, I., Insel, G., Karaca, C., Orhon, D., 2016.
balances: a conceptual framework to understand the limits of municipal
Toward a novel membrane process for organic carbon removal—fate of slowly
wastewater treatment. Water Sci. Technol. 64, 2294–2301.
biodegradable substrate in super fast membrane bioreactor. Environ. Sci. Pollut.
Gebreeyessus, G.D., Jenicek, P., 2016. Thermophilic versus Mesophilic anaerobic
R. 23, 16230–16240.
digestion of sewage sludge: a comparative review. Bioengineering 3, 15.
226 C. Karaca et al. / Waste Management 78 (2018) 217–226

Sözen, S., Basaran, S.T., Ergal, I., Karaca, C., Alli, B., Razbonyali, C., Ubay-Cokgor, E., Wei, Y., Van Houten, R.T., Borger, A.R., Eikelboom, D.H., Fan, Y., 2003. Minimization
Orhon, D., 2017. Super fast membrane bioreactor: a novel process maximizing of excess sludge production for biological wastewater treatment. Water Res. 37,
energy recovery potential in the treatment of complex synthetic substrate and 4453–4467.
domestic sewage. J. Membr. Sci. 545, 337–347. Yagci, N., Novak, J.T., Randall, C.W., Orhon, D., 2015. The effect of iron dosing on
Dümpelmann, R., Richarz, W., Stammbach, M.R., 1991. Kinetic studies of the reducing waste activated sludge in the oxic-settling-anoxic process.
pyrolysis of sewage sludge by TGA and comparison with fluidized beds. Can. J. Bioresource Technol. 193, 213–218.
Chem. Eng. 69, 953–963. Yaman, S., 2004. Pyrolysis of biomass to produce fuels and chemical feedstocks.
Svardal, K., Kroiss, H., 2011. Energy requirements for waste water treatment. Water Energy Convers. Manage. 45, 651–667.
Sci. Technol. 64 (6), 1355–1361. Zaimes, G.G., Soratana, K., Harden, C.L., Landis, A.E., Khanna, V., 2015. Biofuels via
Tas, D.O., Karahan, O., Övez, S., Orhon, D., Spanjers, H., 2009. Biodegradability and fast pyrolysis of perennial grasses: a life cycle evaluation of energy
denitrification potential of settleable chemical oxygen demand in domestic consumption and greenhouse gas emissions. Environ. Sci. Technol. 49, 10007–
wastewater. Water Environ. Res. 81, 715–727. 10018.
Wagenaar, B.M., Kuipers, J.A.M., Prins, W., van Swaaij, W.P.M., 1993. The rotating Zhang, B., Xiong, S., Xiao, B., Yu, D., Jia, X., 2011. Mechanism of wet sewage sludge
cone flash pyrolysis reactor. In: Advances in Thermochemical Biomass pyrolysis in a tubular furnace. Int. J. Hydrogen Energy 36, 355–363.
Conversion. Springer, Dordrecht. pp. 1122–1133.