Waste Management 56 (2016) 530–539

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

Conversion of poultry wastes into energy feedstocks

Ismail Cem Kantarli a,⇑, Arzu Kabadayi b, Suat Ucar c, Jale Yanik b
a
Ege University, Ataturk Medical Technology Vocational Training School, 35100, Bornova, Izmir, Turkey
b
Ege University, Faculty of Science, Department of Chemistry, 35100, Bornova, Izmir, Turkey
c
Dokuz Eylul University, Izmir Vocational School, Chemistry Technology Program, 35160 Izmir, Turkey

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

Article history: In this study, conversion of wastes from poultry farming and industry into biochar and bio-oil via
Received 4 August 2015 thermochemical processes was investigated. Fuel characteristics and chemical structure of biochars
Revised 23 June 2016 and bio-oils have been investigated using standard fuel analysis and spectroscopic methods. Biochars
Accepted 12 July 2016
were produced from poultry litter through both hydrothermal carbonization (sub-critical water,
Available online 18 July 2016
175–250 °C) and pyrolysis over a temperature range between 250 and 500 °C. In comparison to
hydrothermal carbonization, pyrolysis at lower temperatures produced biochar with greater energy yield
Keywords:
due to the higher mass yield. Biochars obtained by both processes were comparable to coal.
Hydrothermal conversion
Pyrolysis
Hydrothermal liquefaction of poultry meal at different temperatures (200–325 °C) was conducted and
Poultry waste compared to optimize its process conditions. Higher temperatures favored the formation of bio-crude
Bio-oil oil, with a maximum yield of 35 wt.% at 300 °C. The higher heating values of bio-oils showed that
Biochar bio-oil could be a potential source of synthetic fuels. However, elemental analysis demonstrated the high
nitrogen content of bio-oils. Therefore, bio-oils obtained from hydrothermal liquefaction of poultry meal
should be upgraded for utilization as a transport and heating fuel.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction
According to the Food and Agriculture Organization of the
United Nations (FAO), poultry now account for over 80% of all live-
stock (FAO, 2015a). The poultry industry produced approximately
23 billion poultry in 2013 all over the world (FAO, 2015b). Today,
poultry are mostly raised in large farms. Due to the intensive poul-
try farming, poultry litter raise serious concerns about treatment
and disposal. It is traditionally used as fertilizer, but potential envi-
ronmental problems such as spread of pathogens (Gerba and
Smith, 2005) and emission of greenhouse gases and odorous com-
pounds are reported due to its overuse as fertilizer (Font-Palma,
2012). The other waste produced in a huge amount by the poultry
industry is poultry meal. It consists of ground, rendered, clean
parts of poultry carcasses and can contain bones, offal, undevel-
oped eggs, and in a few cases, feathers, that are unavoidable parts
in the poultry meat processing (El-Boushi and van der Poel, 2000).
It was used in formulated animal feed, but today it can be only
used in formulated pet feed according to EU Regulation
1774/2002 (European Community, 2002). Therefore, the poultry
industry is facing difficulties in the proper treatment of surplus
⇑ Corresponding author.
E-mail address: ismail.cem.kantarli@ege.edu.tr (I.C. Kantarli).
poultry litter and meal and seeking an alternative technology for
the utilization of these wastes.
Existing technologies such as combustion, anaerobic digestion,
gasification, pyrolysis and hydrothermal conversion may be an
alternative way for proper management of the wastes from poultry
industry. Direct combustion would not be suitable due to the high
water and nitrogen contents of these wastes. Also, anaerobic diges-
tion may not be a good alternative due to the high nitrogen content
of poultry wastes which would inhibit microbial activities
(Yanagida et al., 2007). The use of these wastes as feedstock in
energy production may be of great interest both economically
and environmentally. Hydrothermal conversion has received
increasing attention due to the possibility of processing wet bio-
mass feedstock by eliminating the energy-intensive step of drying
biomass (Libra et al., 2011). It involves the application of heat to
biomass in a closed aqueous medium under autogenic pressure.
Depending on the temperature range, either solid, liquid or gas-
eous products are formed predominately by hydrothermal conver-
sion (Kruse et al., 2009). If hydrothermal conversion is applied in
the temperature range between 160 and 250 °C, mainly a carbon-
rich solid product, named biochar, is formed (Kruse et al., 2013).
The process is referred to as hydrothermal carbonization (HTC)
and was verified as an effective way to densify the energy content
of biomass with high water content (Zhao et al., 2014). Biochar

http://dx.doi.org/10.1016/j.wasman.2016.07.019
0956-053X/Ó 2016 Elsevier Ltd. All rights reserved.
 I.C. Kantarli et al. / Waste Management 56 (2016) 530–539
produced during HTC is characterized with enhanced fuel proper-
ties such as increased carbon content, higher homogeneity, better
grindability, and hydrophobic behavior (Sermyagina et al., 2015).
If hydrothermal conversion is applied in the temperature range
of 225–350 °C, a high-viscous oil, named bio-oil, is formed. In this
case, the process is referred to as hydrothermal liquefaction (HTL)
(Elliott et al., 2015; Kruse et al., 2013). Bio-oil can be converted into
liquid petroleum fuels, such as diesel and gasoline by upgrading
(Tekin et al., 2014). On the other hand, gasification reactions are
dominant under near- and supercritical-water conditions.
Hydrothermal gasification is mostly preferred for methane and
hydrogen production (Savage et al., 2010).
In the literature, the application of hydrothermal processes to
different types of biomass such as woody biomass (Nanda et al.,
2016a; Lynam et al., 2015; Chan et al., 2014; Hoekman et al.,
2011; Liu et al., 2013; Qu et al., 2003; Sevilla et al., 2011; Xiao
et al., 2012; Wiedner et al., 2013), agricultural wastes (Lynam
et al., 2015; Sevilla et al., 2011; Xiao et al., 2012; Román et al.,
2012; Pala et al., 2014), food wastes (Nanda et al., 2016b; Li
et al., 2013; Lu et al., 2012), algal biomass (Elsayed et al., 2016;
Eboibi et al., 2014; Jena et al., 2011; Heilmann et al., 2010), aquatic
plant (Poerschmann et al., 2015), sewage sludge (He et al., 2013;
Parshetti et al., 2013; Chen et al., 2013; Zhang et al., 2010), paper
waste sludge (Louw et al., 2016) and manure of different livestock
(Cao et al., 2011; Xiu et al., 2010; Yin et al., 2010) has been dis-
cussed by many authors. However, there are few studies on
hydrothermal conversion of poultry wastes in the literature. These
studies include the hydrothermal gasification and carbonization.
For instance, Nakamura et al. (2008) and Yanagida et al. (2007)
studied the hydrothermal gasification of poultry litter in the
presence of activated carbon catalyst and obtained gas products
consisting mainly of H2, CO2 and CH4, besides NH3. Similarly, in
the hydrothermal gasification of poultry litter in the presence of
wood, the organic matter in the poultry litter was converted into
gases mainly H2, CO2, and CH4 (Yong and Matsumura, 2012).
In another study, Oliveira et al. (2013) carried out the HTC of
poultry litter at 180 °C for 4 h. The resultant biochar had a calorific
value of 24 MJ/kg which was similar to that of bitumen-rich brown
coal. In contrast to hydrothermal processes, a number of studies
relating to pyrolysis of poultry litter exist in the literature (Chan
et al., 2008; Song and Guo, 2012; Azargohar et al., 2014; Novak
et al., 2014; Van Zwieten et al., 2013; Ameloot et al., 2015;
Rombolá et al., 2015). These studies focused on the physical and
chemical characteristics of the biochars obtained from poultry
litter for use as soil amendment.
In this study, conversion of poultry wastes, poultry meal and
poultry litter, into biochar and/or bio-oil was investigated in order
to find a feasible approach for their disposal and to obtain suitable
energy feedstocks. In this context, hydrothermal carbonization of
and comparatively pyrolysis of poultry litter were performed to
produce biochar. Hydrothermal liquefaction of poultry meal was
performed to produce bio-oil. Fuel characteristics and chemical
structure of biochars and bio-oils were investigated using standard
fuel analysis and spectroscopic methods. To the best of our knowl-
edge, no study on hydrothermal conversion of poultry meal exists
in the literature.
2. Methods
2.1. Materials
Poultry wastes were kindly provided by CP Group, Izmir, Tur-
key. Poultry meal (<1 mm) was used as received, whereas poultry
litter was previously dried at room temperature and ground to
<1.5 mm, then dried in a drying oven at 105 °C overnight. The char-
acteristics of feedstocks are given in Table 1.
531
Table 1
Characteristics of poultry wastes.
Poultry meal Poultry litter
Proximate analysis, (wt.%)
Moisture 6.6 8.2
Volatile matter 78.4 60.2
Ash 12.9 15.4
Ultimate analysis,(dry basis, wt.%)
C 52.1 40.0
H 7.4 5.4
N 11.6 5.6
S 0.5 0.1
O* 15.5 33.5
Protein 65.0 33.1
Oil 16 N.D.
HHV (MJ/kg) 24.7 16.0
N.D.: not determined.
*
Calculated by difference.
2.2. Hydrothermal conversion experiments
Hydrothermal conversion experiments were carried out in a
100 mL stainless steel shaking autoclave under autogenic pres-
sure. For a typical run, a mixture of poultry meal or poultry lit-
ter and deionized water (waste/water ratio of 20:80) was
loaded into the autoclave. The autoclave was sealed and purged
with nitrogen. It was heated to the desired temperature at a
rate of 5 °C min
1 and was held at this temperature for the
required duration. In the case of HTC experiments, different
reaction times (0–60 min) and temperatures (175–250 °C) were
tested. HTL experiments were conducted at different tempera-
tures (200–325 °C) for a reaction time of 30 min. At the end
of the hydrothermal process, the reactor was rapidly cooled
down to room temperature. In HTC, after gaseous products
were vented into the atmosphere, the solid residue (biochar)
was separated from reactor content by filtration and washed
with 100 ml distilled water and then dried at 105 °C for 24 h
and weighed. The filtrates (aqueous phase) were bottled for
further analysis. In HTL, gaseous products were collected in a
volumetric flask for measuring their volume and GC analysis.
The reactor content was washed with dichloromethane and
filtered to separate the solid residue (char). The filtrate was
separated into dichloromethane phase and aqueous phase by a
separatory funnel. After evaporation of dichloromethane at
30 °C using a rotary vacuum evaporator, the residue was
weighed as bio-oil. Char was weighed after being dried at
105 °C for 24 h. The gas yield was calculated depending on its
volume and GC analysis. The water soluble product yield was
calculated by following equation:
water soluble product yield ðwt:%Þ
¼ 100-char yield ðwt:%Þ-bio-oil yield ðwt:%Þ-gas yield ðwt:%Þ:
2.3. Pyrolysis experiments
The pyrolysis experiments were carried out in a vertical fixed
bed design reactor. In a typical run, 50 g of poultry litter was placed
into the reactor. The system was heated to the desired temperature
(250–500 °C) at a heating rate of 5 °C min
1, and held at this tem-
perature for 1 h. The volatile products were swept by nitrogen gas
with a flow rate of 25 mL min
1 from reactor to collection flasks
cooled with ice where the liquid products were condensed in the
traps. The non-condensable volatiles (gases) were vented to the
atmosphere. The solid residue (biochar) was weighed in order to
calculate the biochar yield.
532 I.C. Kantarli et al. / Waste Management 56 (2016) 530–539
2.4. Feedstock and product characterization
Thermogravimetric analysis of feedstocks and biochar samples
was performed in a thermogravimetric analyzer (Perkin Elmer Dia-
mond TG/DTA) under nitrogen atmosphere. The flow rate of purge
gas (pure N2, 99.99%) was kept at 200 mL min
1. The sample was
heated from the ambient temperature up to 900 °C with a heating
rate of 10 °C min
1.
The elemental analysis of feedstocks, biochars and bio-oils was
carried out by a LECO CHNS 932 elemental analyzer according to
ASTM D5291-96. The protein content of feedstocks was deter-
mined using a protein analyzer (INKJEL M). The lipid content of
poultry meal was determined by extraction with hexane. Proxi-
mate analysis of feedstocks and biochars was made according to
the standard analysis methods: ASTM D3174-04 for ash analysis
and ASTM D3175-89 for volatile matter. The higher heating values
(HHV) of feedstocks and biochars produced by pyrolysis were
determined using an IKA C-2000 basic model calorimeter accord-
ing to ASTM D240-02. The HHV of the biochars produced by HTC
was calculated by the following correlation proposed by
Channiwala and Parikh (2002):

1
HHV ðMJ kg Þ ¼ 0:3491  C þ 1:1783  H þ 0:1005  S
0:1034
 O
0:015  N
0:0211 A
where C, H, S, O, N and A are the weight percents of carbon, hydro-
gen, sulfur, oxygen, nitrogen and ash, respectively.
Energy densification is the energy content of biochar divided by
the energy content of feedstock, while energy yield is defined as
the biochar mass yield multiplied by the energy densification ratio
(Yan and Acharjee, 2009). Energy densification and energy yield
were calculated for all biochar samples.
HHVs of the bio-oils were calculated by the following correla-
tion proposed by Friedl et al. (2005):

1
HHV ðMJ kg Þ ¼ ð3:55  C2
232  C
2230  H þ 51:2  C  H
þ 131  N þ 20600Þ  10
3
where C, H and N are the weight percents of carbon, hydrogen and
nitrogen in bio-oil, respectively.
The infrared spectra of biochars and bio-oils were recorded with
a Perkin Elmer Spectrum 100 FTIR spectrometer. FTIR spectrometer
was coupled with Attenuated Total Reflectance (ATR) in the analysis
of biochars. The total organic carbon (TOC) content in the aqueous
phase was determined using a TOC analyser (HachLange IL550-
TOC-TN). 1H NMR spectrum of bio-oil samples in CDCl3 were
recorded at 400 MHz, on an NMR spectrometer (MERCURY plus-
AS 400) at 25 °C. GC-MS spectra of bio-oil samples were obtained
using a Thermo DSQ model Gas Chromatograph with a thin film
TG-1701 MS capillary column (60 m  0.25 mm i.d.; 0.25 lm film
thickness). The oven temperature was programmed at 45 °C for
4 min, then increased to 130 °C at a heating rate of 3 °C/min, to
230 °C at a heating rate of 2 °C/min and to 280 °C at a heating rate
of 3 °C/min. The injector temperature was 250 °C and the splitless
injection size was 1 lL. The ion source temperature was 280 °C for
the mass selective detector. The compounds in bio-oil samples
were identified using the NIST Mass Spectral Database. Gaseous
products were analyzed by a refinery gas analyzer (RGA).
3. Results and discussion
3.1. Feedstock characteristics
Both poultry litter and poultry meal had lower fixed carbon,
higher moisture content and volatile matter content than those
of coal as can be seen from Table 1. Due to its high carbon content
and lower ash content, poultry meal had higher heating value than
poultry litter. It is worth noting that poultry meal had an oil con-
tent of 16 wt.%, which makes it a suitable feedstock for production
of bio-oil, but its protein content might raise questions about the
quality of bio-oil.
To understand the thermal conversion behavior under the inert
atmosphere or pyrolysis behavior of both feedstocks, thermogravi-
metric analysis was systematically carried out at a heating rate of
10 °C min
1. The weight loss (TG curve) and derivative weight
loss (DTG curve) for poultry meal and poultry litter are given in
Supplementary 1.
For poultry meal, one DTG curve (plus drying step) was
observed as a peak in the range of 200–500 °C, which corre-
sponds to the main pyrolytic decomposition step. The maximum
decomposition rate was reached at 325 °C. Similar results were
obtained in the thermal degradation of wastes rich in protein,
such as animal meat and bone meal (Chaala and Roy, 2003;
Ayllón et al., 2005) and chicken feathers (Brebu and Spiridon,
2011). The weight loss during main pyrolytic decomposition
was approximately 71% of total weight. On the other hand, the
DTG curve of poultry litter was divided into two main regions
(plus drying step and carbonates decomposition step). The first
pyrolytic decomposition region, in the range of 200–360 °C,
was observed as a peak centered at 284 °C. This region is attrib-
uted to decomposition of holocellulose. The second pyrolytic
decomposition region, including two small shoulders in the
range of 360–480 °C, was associated with manure (Giuntoli
et al., 2009). It was inferred that the curve related to lignin
decomposition was overlapped with the other curves between
200 and 500 °C. Further decomposition of inorganics (mainly car-
bonates) occurred at higher temperatures (greater than 600 °C)
(Florin et al., 2009). The final residue was 32% of the total
weight.
3.2. Preliminary pyrolysis and hydrothermal conversion studies
Preliminary pyrolysis and hydrothermal conversion experi-
ments carried out with both feedstocks, revealed important results
which were decisive for planning this study. The following results
were obtained:
i. In hydrothermal conversion of poultry litter carried out at
temperatures from 200 to 250 °C, the bio-oil yield was very
low (5–6.4 wt.%) because of lignocellulosic bedding material
in poultry litter. Therefore, hydrothermal liquefaction of
poultry litter was not studied in detail.
ii. In hydrothermal conversion of poultry meal, the biochar
yield decreased from 60 to 28 wt.% as the temperature
increased from 160 to 200 °C. Almost no biochar was
obtained above 200 °C because of the high protein con-
tent of poultry meal. Although the biochar yield was
high at 160 and 175 °C, the TG curves of raw material
and both biochars are similar to each other, showing
ineffective carbonization of feedstock. Therefore,
hydrothermal carbonization of poultry meal was not
studied in detail.
iii. In pyrolysis of poultry meal, it was not possible to fix the
temperature at low temperatures such as 250 and 300 °C,
because the degradation reactions were highly exothermic.
These experiments could be carried out at only high temper-
atures (400 and 500 °C), but the char yields were signifi-
cantly low at these temperatures. Therefore, biochars
derived from poultry meal by pyrolysis were not included
in the scope of this study.
 I.C. Kantarli et al. / Waste Management 56 (2016) 530–539
3.3. Pyrolysis and hydrothermal carbonization
3.3.1. Biochar yields
A series of HTC experiments were carried out to determine the
effects of reaction time and reaction temperature on the yield and
characteristics of biochars derived from poultry litter. In the first
set of experiments, the reaction temperature was held at 225 °C,
while the reaction time was varied from 0 to 60 min. In the second
set of experiments, the reaction temperature was varied between
175 and 250 °C, while the reaction time was kept constant. On
the other hand, in the pyrolysis experiments, the effect of reaction
temperature on the yield and characteristics of biochars derived
from poultry litter was investigated. The biochar yields for both
HTC and pyrolysis are shown in Fig. 1. Biochar samples, given in
Table 1, were defined as following the ‘‘Process–Temperature–Ti
me” sequence (e.g. HTC-225-0 stands for hydrothermal carboniza-
tion conducted at 225 °C for 0 min, whereas T-300-60 stands for
pyrolysis conducted at 300 °C for 60 min).
In the case of HTC, the reaction time had almost no effect on
biochar yield; yields changed slightly between 38 and 40 wt.%.
On the other hand, biochar yield decreased gradually from 44 to
36 wt.% with the increase of temperature from 175 to 250 °C
(Fig. 1). This decrease was more distinctive when the temperature
increased from 225 to 250 °C. The low yields at high temperatures
might be attributed to the enhanced decomposition of poultry lit-
ter and/or secondary decomposition of char which leads to gasifi-
cation and liquefaction reactions at higher temperatures (Pala
et al., 2014). In previous studies (Hoekman et al., 2011; Román
et al., 2012; Lynam et al., 2015; Pala et al., 2014), it was similarly
observed that the reaction temperature had a stronger effect on
HTC product distributions than the reaction time.
The biochar yields obtained from HTC of poultry litter in this
study are lower than the biochar yields obtained from HTC of dif-
ferent kinds of biomass in the literature. For example, Hoekman
et al. (2011) reported that the biochar yield from a mix of Jeffrey
and White Fir varied from 70 to 50 wt.% over the temperature
range of 215–255 °C. In other similar studies, the reported biochar
yields were 90–45 wt.% (within the temperature range of 150–
250 °C from coconut fiber and eucalyptus leaves) (Liu et al.,
2013); 54 wt.% (at 200 °C for 4 h from sewage sludge) (He et al.,
2013); 51 wt.% (at 240 °C from aquatic plant Elodea nuttallii)
70
60
50
Yield, wt. %
40
30
20
10
0
HTC-175-30 HTC-200-30 HTC-225-0 HTC-225-15 HTC-225-30 HTC-225-60 HTC-250-30
Fig. 1. Biochar yields for hydrothermal carbonization and pyrolysis of poultry litter.
533
(Poerschmann et al., 2015) and 75–49 wt.% (within the tempera-
ture range of 180–230 °C from Olive residues) (Wiedner et al.,
2013). The lower biochar yields obtained in this study than those
of obtained from the other biomasses tested in the literature must
have been due to the compositional difference between poultry lit-
ter and the other biomasses. Possibly manure and protein contents
in poultry litter are easily hydrolyzed into water-soluble frag-
ments, mainly simple amino acids, which do not involve in biochar
formation (Cao et al., 2011). In a similar study of Oliveira et al.
(2013) on HTC of poultry litter, biochar yield obtained from poultry
litter at 180 °C for 4 h was 52.5 wt.% and higher than that of
obtained at 175 °C for 30 min in this study. This difference in bio-
char yields was attributed to the difference in composition of both
poultry litters.
In the case of pyrolysis, biochar yield decreased with the
increase of temperature (Fig. 1), as expected. As can be seen from
Fig. 1, the biochar yields from pyrolysis (6300 °C) were higher than
that of from HTC. The reason may be explained as follows. In the
case of HTC, decomposition of biomass is dominated by reaction
mechanisms similar to those in pyrolysis including hydrolysis,
dehydration, decarboxylation, aromatization and recondensation
(Funke and Ziegler, 2010; Peterson et al., 2008). However, decom-
position of biomass in HTC is initiated by hydrolysis, which has
lower activation energy than most of the pyrolytic decomposition
reactions (Libra et al., 2011). Therefore, HTC yielded less biochar,
due to higher reactivity of biomass and less occurrence of recon-
densation reactions under aqueous conditions. Similarly, in our
previous study with a lignocellulosic biomass (grape pomace), bio-
char yields from pyrolysis (6300 °C) were found to be higher than
that of from HTC (Pala et al., 2014).
3.3.2. Carbon and nitrogen distribution
In the HTC process, carbon distribution among the solid,
aqueous and gas phases was calculated according to elemental
analysis of biochars and TOC analysis of aqueous phases. The
carbon distribution in gas product was calculated from difference.
Carbon distribution in products is given in Fig. 2. Thus, carbon
distribution in product was calculated as,
wt:% ¼ ðcarbon amount in product=carbon amount in poultry litterÞ
 100:
T-250-60 T-300-60 T-400-60 T-500-60
534 I.C. Kantarli et al. / Waste Management 56 (2016) 530–539

and oxygen content of biochars decreased significantly, while

100
hydrogen content of biochars changed slightly implying that car-
bonization took place. In the case of pyrolysis experiments, carbon
80
gas content of biochar first increased up to 300 °C, but then decreased
with increasing temperature due to the increasing ash content of
wt. %

60
biochars.
aqueous
phase The biochars produced by HTC in the temperature range
40
between 175 and 250 °C had H/C ratios of 1.52–1.20 and O/C ratios
biochar of 0.52–0.27. The decreasing tendency of H/C ratios and O/C ratios
20
basically corresponded to dehydration and decarboxylation pro-
cesses. These ratios were found close to those obtained in previous
0
studies carried out with pig manure and poultry litter (Table 3). On
HTC-175-30 HTC-200-30 HTC-225-30 HTC-250-30
the other hand, they are different from those obtained with ligno-
Fig. 2. Carbon distribution in hydrothermal carbonization. cellulosic wastes, such as grape pomace, barley straw, coconut
fiber, Eucalyptus leaves and sawdust, corn stalk, and Tamarix ramo-
sissima (a forest waste) (Table 3).
As seen from Fig. 2, half of the carbon in poultry litter (46– The biochars produced by pyrolysis had H/C ratios of 1.16–0.56
50 wt.%) was retained in the biochars. This result is not consistent and O/C ratio of 0.31–0.11. Azargohar et al. (2014) obtained bio-
with our previous study associated with a lignocellulosic biomass char by pyrolysis of poultry litter at 400 °C with H/C ratio of 0.28
(Pala et al., 2014). In our previous study, most of the carbon in bio- and O/C ratio of 0.09. In their study, when the pyrolysis tempera-
mass (65–73 wt.%) was retained in biochar. This difference may be ture was increased to 475 °C and higher, H/C ratio of biochar
due to the high protein content in poultry litter. Based on the liter- increased to 0.43 for biochar obtained at 475 °C and did not change
ature (Yanik et al., 2007), it can be deduced that proteins can be above 475 °C.
easily degraded in sub-critical water and do not much participate Van Krevelen diagram is a useful tool to assess the origin of
in the char formation reactions. Above 200 °C, distribution of car- coals and coal derivatives. In the present study, this diagram was
bon in the gas phase increased, while the distribution of carbon drawn based on H/C and O/C atomic ratios of biomass and corre-
in aqueous phase decreased from 39 to 28 wt.%. This shows that sponding biochars in order to examine the changes in atomic C,
the organics in the aqueous phase were mainly degraded into gas- H, and O compositions during carbonization (Fig. 3). Typical ranges
eous compounds by increasing the temperature. In other words, for anthracite, bituminous coal, lignite and peat were also depicted
amino acids formed from protein/manure degradation produced in this diagram. The positions of the HTC biochars obtained at low
low-molecular-weight carboxylic acid which might have further temperatures (175–200 °C) on this diagram were close to or in the
produced gases by decarboxylation. range of peat, whereas the positions of the HTC biochars obtained
On the other hand, in pyrolysis at lower temperatures, the per- at 225 and 250 °C were close to or in the range of lignite. On the
cent of carbon in feedstock (between 80 and 84 wt.%) retained in other hand, the positions of the biochars obtained by pyrolysis at
biochar was found much higher in comparison to HTC. At higher temperatures higher than 250 °C were in the range of bituminous
pyrolysis temperatures (400 and 500 °C), the percent of carbon in
feedstock retained in biochar decreased to the range between 41
and 51 wt.%. In the case of distribution of nitrogen in feedstock, Table 3
Reported H/C and O/C ratios for biochars obtained from different biomasses by
between 22.3 and 27.4 wt.% of nitrogen was retained in HTC bio-
hydrothermal carbonization.
char, while between 30.6 and 72.8 wt.% of nitrogen was retained
in biochar from pyrolysis. This difference might also be due to Biomass Hydrothermal H/C O/C Literature
carbonization
the hydrolysis of protein and nitrogenous compounds under
conditions
hydrothermal conditions.
Solid pig manure 250 °C, 20 h 1.37 0.25 Cao et al. (2011)
Poultry litter 180 °C, 4h 1.35 0.25 Oliveira et al. (2013)
3.3.3. Fuel characteristics of biochars Grape pomace 250 °C, 0.5 h 1.03 0.26 Pala et al. (2014)
Proximate, elemental, and energy analysis results of biochars Eucalyptus sawdust 250 °C, 2h 0.81 0.27 Sevilla et al. (2011)
obtained from both HTC and pyrolysis are presented in Table 2. Barley straw 250 °C, 2h 0.80 0.20 Sevilla et al. (2011)
As expected, volatile matter content of biochars decreased with Coconut fiber 250 °C, 0.5 h 0.93 0.30 Liu et al. (2013)
Eucalyptus leaves 250 °C, 0.5 h 1.05 0.37 Liu et al. (2013)
increasing temperature, showing that the stability of the organic Corn stalk 250 °C, 4h 0.94 0.17 Xiao et al. (2012)
carbon in biochars was improved. In HTC of poultry litter, with Tamarix Ramosissima 250 °C, 4h 0.90 0.22 Xiao et al. (2012)
increase in temperature, carbon content of biochars increased

Table 2
Some properties and energy analysis of biochars.

Proximate analysis (wt.%) Elemental analysis (wt.%) Atomic ratio HHV (MJ/kg) Energy densification Energy yield (%)
Ash Volatile matter C H N S O* O/C H/C
HTC-175-30 22.5 69.5 41.6 5.3 3.5 0.8 26.3 0.52 1.52 17.6 1.10 48.2
HTC-200-30 20.0 59.0 43.4 5.1 3.0 0.6 28.0 0.50 1.39 17.8 1.11 46.3
HTC-225-30 22.6 60.0 50.2 5.6 3.6 0.6 17.5 0.28 1.32 21.8 1.36 54.0
HTC-250-30 23.3 49.1 50.4 5.1 4.0 0.4 16.7 0.27 1.20 21.3 1.33 47.5
T-250-60 23.4 52.1 46.3 4.5 6.7 0.1 19.0 0.31 1.16 18.8 1.17 77.0
T-300-60 27.2 38.9 52.1 3.9 7.3 0.1 9.4 0.14 0.89 20.3 1.26 77.5
T-400-60 36.2 18.6 48.0 3.1 5.9 – 6.8 0.11 0.77 18.3 1.05 42.5
T-500-60 42.1 21.0 44.8 2.1 4.7 – 6.3 0.11 0.56 15.8 0.89 36.6
*
Calculated from difference.
 I.C. Kantarli et al. / Waste Management 56 (2016) 530–539 535

1.80 FTIR spectra of poultry litter and biochars obtained by both HTC
1.60 Poultry litter and pyrolysis at higher temperature was assigned to amide-II band
HTC-175-30
due to N-H bending vibrations (Schnitzer et al., 2007). An intensive
1.40 HTC-200-30
band was observed at 1450 cm
1 in the FTIR spectra of biochars
H/C atomic ratioa

HTC-225-30
1.20 HTC-250-30
T-250-60
1.00
T-300-60
0.80 T-400-60
0.60 T-500-60
0.40
0.20
0.00
0.00 0.10 0.20 0.30 0.40
O/C atomic ratio
Fig. 3. Atomic H/C and O/C ratios of poultry litter and its derived-biochars (Van
Kreevelen diagram).
coal. Although the biochars were close to coal, they had higher
nitrogen content than the limit value (63.0%) for solid biofuels
according to ISO 17225-1:2014.
Biochar is mainly produced with the aim of densification of
energy in feedstock. As summarized in Table 2, the energy densifi-
cation ratio of HTC biochars increased remarkably by increasing of
temperature from 200 to 225 °C, and then slightly decreased above
225 °C. Similarly, the energy yield of HTC biochar increased by
increasing of temperature from 200 to 225 °C, but above 225 °C it
decreased remarkably. This decrease was certainly due to the
decreased mass yield. In the literature, it was reported that the
energy yield of biochars obtained from HTC of a mix of Jeffrey pine
and white fir decreased from 77 to 70% over the temperature range
of 215–295 °C (Hoekman et al., 2011). The energy yield of biochars
obtained from HTC of coconut fiber and eucalyptus leaves
decreased from 76.7 to 65.0% and from 87.3 to 61.3% within the
temperature range of 220–300 °C, respectively (Liu et al., 2013).
Comparison of the energy yield of HTC of poultry litter in this study
with that of HTC of poultry litter in a previous study revealed that
the energy yield range of 46–54% obtained in this study is lower
than the energy yield of 67.6% obtained in the previous study
(Oliveira et al., 2013). The different observations for energy yield
obtained by HTC, while it was not observed in the FTIR spectra of
neither poultry litter nor biochars obtained by pyrolysis. This band
was assigned to CH2 deformation. The band at 1313 cm
1 observed
in the FTIR spectra of poultry litter and biochars obtained by both
HTC and pyrolysis was assigned to CAN stretching vibration of pri-
mary amines. The band at 1160 cm
1 in the FTIR spectra of bio-
chars obtained by pyrolysis was assigned to asymmetric CAO
stretching characteristic of CAOAC in cellulose and hemicelluloses
0.50 0.60 0.70 0.80
(Cantrell et al., 2012). The band at 1050–1000 cm
1, which was
observed in the FTIR spectra of poultry litter and biochars obtained
by HTC and not observed for biochars obtained by pyrolysis, was
assigned to CAO stretching of carbohydrates. The bands at 950–
700 cm
1 were assigned to aromatic CAH bending vibration
(Sevilla et al., 2011). In comparison with biochars obtained by
HTC, the increase in the intensity of the band at 750–700 cm
1
for biochars obtained by pyrolysis, suggests that pyrolysis leads
to formation of higher amount of aromatic rings. The FTIR spectra
demonstrated that the biochars obtained by pyrolysis were more
aromatic in nature. Cao et al. (2011) states that the char obtained
by pyrolysis usually shows predominant aromatics, whereas the
biochar produced by HTC shows mainly aliphatics.
3.3.5. Thermal degradation behavior of biochars
Fig. 4a and b shows the TG/DTG profiles of biochars. The weight
of residue material was the highest for T-300-60. This is due to
both the higher ash and fixed carbon contents of T-300-60 than
those of other biochars. Comparison of the DTG curves of biochars
shows characteristic shifting of DTG peak temperatures to higher
temperatures. For HTC biochars, degradation occurs over a wider
100
80
HTC-175-30
weight, %

were attributed to the differences in composition of poultry litters 60 HTC-200-30

and HTC conditions. On the other hand, for the biochar obtained HTC-225-30
from pyrolysis, the energy densification ratio increased remarkably 40
HTC-250-30
by increasing of temperature from 250 to 300 °C and then signifi-
T-250-60
cantly decreased. This decrease is due to the high ash content lead- 20
ing to low HHV. Besides energy densification, a sharp decrease in T-300-60 (a)
energy yield was observed above 300 °C due to both low mass yield 0
and HHV. Overall, comparison of two processes reveals that the 0 100 200 300 400 500 600 700 800 900
highest energy yield was obtained by pyrolysis process at 250 Temperature,°C
and 300 °C, as a result of higher mass yield compared to HTC. On
the other hand, HTC was found more successful at energy 10
densification. 9
HTC-175-30
8 HTC-200-30
3.3.4. FTIR spectra of biochars
7 HTC-225-30
The FTIR spectra of biochars gives information on chemical
6 HTC-250-30
-dm / dt

composition of biochars. The changes in the chemical structure T-250-60

of the biochars depending on the temperature and process type 5
T-300-60
are given in Supplementary 2. 4
In the FTIR spectra of biochars obtained by both HTC and pyrol- 3
ysis, the band at 2920 cm
1 was assigned to CH3-stretching. This 2
band was not observed in the FTIR spectrum of poultry litter. 1 (b)
Intensive band observed in the FTIR spectra of poultry litter and 0
biochars obtained by both HTC and pyrolysis at 1650 cm
1 was 0 100 200 300 400 500 600 700 800 900
assigned to amide-I band due to carbonyl stretching vibration in Temperature,°C
the peptide bond (Schnitzer et al., 2007; Cantrell et al., 2012;
Jiang et al., 2004). The band at nearly 1550 cm
1 observed in the Fig. 4. (a) TG curves of biochars. (b) DTG curves of biochars.
536
temperature range, with only one main peak being observed. How-
ever, for biochars from pyrolysis, two peaks are observed. In HTC
and pyrolysis at 250 °C, some part of holocellulose decomposed.
However, in the case of pyrolysis at 300 °C, we can suggest that
most of the biochar holocellulose decomposed and only char from
degradation of manure and lignin remained.
The most significant difference between biochars obtained by
HTC and pyrolysis is in the intensity of DTG peaks. The higher
DTG peaks in HTC biochars shows that degradation of these bio-
chars took place easily and faster. Based on this result, we can sug-
gest that HTC produced less stable biochars than pyrolysis.
3.4. Hydrothermal liquefaction
Hydrothermal liquefaction (HTL) is a biomass-to-liquid conver-
sion route carried out in water at elevated temperatures and pro-
duces a high energy density organic liquid, bio-oil, as main
product, as well as gaseous, aqueous and solid phase by-
products. Based on the results obtained from preliminary experi-
ments, HTL of poultry meal was aimed to obtain bio-oil and a series
of experiments were carried out in order to investigate the effect of
temperature on the bio-oil yield and quality.
3.4.1. Product distribution
Product distributions obtained from HTL of poultry meal carried
out in the temperature range of 200–325 °C are given in Fig. 5. As
can be seen from Fig. 5, the temperature range 200–225 °C seems
to be critical for degradation of poultry meal. In this temperature
range, the liquid product yield (bio-oil + water soluble products)
significantly increased while the char yield decreased. This shows
that degradation of poultry meal took place mainly between 200
and 225 °C. In other words, hydrolysis of poultry meal constituents
(such as lipids and proteins) into smaller fragments dominates in
this temperature range (Alba et al., 2012).
Rogalinski et al. (2005) and Rogalinski and Brunner (2005) car-
ried out hydrolysis of a model protein (BSA, bovine serum albumin)
and fibrous sclero-proteins like feathers and hair, in a continuous
plug-flow reactor, which resulted in the total liquefaction of pro-
teins leading to formation of amino acids. Production of amino
acids was temperature and residence time dependent. In the
experiments carried out at 250 °C, the amino acid yield increased
up to a residence time of 5 min and then decreased due to decom-
position reactions. In the present study, it seems that bio-oil was
formed through secondary decomposition of products from protein
hydrolysis. Above 225 °C, decrease in the char yield was insignifi-
cant. However, the bio-oil yield continue to increase up to 275 °C
whereas the amount of water-soluble compounds decreased. In
other words, as a result of competition between hydrolysis and
repolymerization, repolymerization of water soluble compounds
70
60
50
Yield, wt.%
char bio-oil gas
40
30
20
10
0
200 225 250 275
Temperature, °C
Fig. 5. Product yields obtained from hydrothermal liquefaction of poultry meal.
I.C. Kantarli et al. / Waste Management 56 (2016) 530–539
into oily compounds occurred dominantly in this temperature
range (Alba et al., 2012). On the other hand, the gas yield remained
unchanged in the temperature range from 200 to 225 °C and then
increased slowly from 1.0 to 4.2 wt.% in the temperature range
from 250 to 325 °C. As seen from Fig. 5, slight decrease in the char
and bio-oil yield and slight increase in the gas yield at 325 °C
implies that gasification will take place at temperatures higher
than 325 °C. It is also given in the literature that the secondary
decompositions leading to formation of gas is dominant at higher
temperatures (Akhtar and Amin, 2011). General trend in HTL of
feedstocks, either algal or lignocellulosic, was observed as follows:
first both bio-oil and water soluble products yields increased with
increasing of temperature at low temperature ranges, and then
bio-oil yield continued to increase with further increase in temper-
ature, whereas water soluble product yield decreased (Jena et al.,
2011; Alba et al., 2012; Eboibi et al., 2014; Qu et al., 2003). For
all the temperatures investigated in this study, water soluble pro-
duct was the major product with yields higher than 54 wt.%. Since
poultry meal has high protein content (65 wt.%), it is not surprising
that water soluble compounds formed in huge amount through
degradation of proteins during HTL. The pH values of aqueous
phase from HTL experiments were in the range of 8–9, showing
that the water soluble degradation products are basic nitrogenous
compounds. Taking this into account, we can suggest that spent
liquor (aqueous phase) from HTL can be used as nitrogenous fertil-
izer, which might make the overall process environmentally
friendly.
Maximum bio-oil yield obtained from poultry meal (35 wt.%) is
comparable to the bio-oil yields obtained from different feedstocks
by HTL process, which are 24 wt.% from swine manure (Xiu et al.,
2010), 38 wt.% from cattle manure (Yin et al., 2010), 40–60 wt.%
from microalgae species (Eboibi et al., 2014; Alba et al., 2012;
Jena et al., 2011), 38 wt.% from palm kernel shell (Chan et al.,
2014), and 24 wt.% from woody biomass (Qu et al., 2003).
3.4.2. Characteristics of bio-oils
3.4.2.1. Fuel characteristics. The bio-oils were dark brown in color
as all bio-oils obtained from biomasses. Elemental analysis and
higher heating value results of HTL bio-oils obtained at different
temperatures are given in Table 4. Bio-oil samples were named
as following the ‘‘Process–Temperature” sequence (e.g. HTL-225
stands for hydrothermal liquefaction conducted at 225 °C).
Elemental analysis results showed that the bio-oils contained
more carbon and hydrogen, and less oxygen and nitrogen than
poultry meal. Since the bio-oils were separated from reaction prod-
ucts by dichloromethane extraction, they contained no water.
Comparing the HHVs of bio-oils obtained from different kinds of
biomass with those of obtained from poultry meal in this study
reveals that HTL of poultry meal produced bio-oils having similar
higher heating value (Xiu et al., 2010; Yin et al., 2010; Xu and
Lad, 2008; Jena et al., 2011; Alba et al., 2012). For example, HHVs
of the bio-oils obtained from HTL of swine manure, cattle manure,
pine sawdust, Spirulina plantesis and Desmodesmus sp. were 36.0,
35.5, 32.3, 39.8, and 36.9 MJ/kg, respectively. However, the high
nitrogen contents in the bio-oils due to the high amount of
water-soluble products
proteins in poultry meal remain a major challenge to producing
Table 4
Elemental composition and higher heating values of bio-oils.
C H N S O HHV (MJ/kg)
HTL-225 66.1 9.4 5.5 1.0 18.0 32.3
300 325
HTL-275 70.5 10.1 7.4 1.0 11.0 36.9
HTL-300 69.0 9.9 6.8 1.4 12.9 35.2
HTL-325 71.9 10.4 6.7 1.2 9.8 38.2
 I.C. Kantarli et al. / Waste Management 56 (2016) 530–539 537

commercial fuels from poultry meal. Therefore, the bio-oils should bio-oils. This represents not only those protons in benzenoids,
be upgraded for utilization as a transport and heating fuel. It must but also those in heteroaromatics containing O and N. Overall,
be noted that the bio-oils obtained from feedstocks having high temperature did not much change the percentages of protons of
nitrogen content, such as manure and algae (Xiu et al., 2010; bio-oils grouped according to chemical shift change.
Jena et al., 2011; Alba et al., 2012), had also similar nitrogen con- By GC-MS analysis, more than 70 peaks were found in the GC/
tent with bio-oils in this study, but they differed in percentage of MS chromatograms. The perfect separation of all the peaks was
nitrogen in feedstocks retained in bio-oil. 11.8–21.5 wt.% of nitro- not possible due to the complex composition of bio-oils. Therefore,
gen in poultry meal retained in bio-oils, while much higher per- some of the compounds were semi quantitatively evaluated. The
centage of nitrogen in swine manure (Xiu et al., 2010) and in typical identified compounds in the bio-oils (HTL-275 and HTL-
microalgae Desmodesmus sp. (Alba et al., 2012) (approximately 325) by GC-MS are presented in Table 6. GC-MS analysis revealed
40 wt.%) retained in bio-oils. that compounds having relatively higher peak area percent
in HTL-275 and HTL-325 bio-oils were trans-2-Methoxy-6-
(formylmethyl) tetrahydropyran, 2-Piperidinone, 2-ethyl piperidine,
3.4.2.2. Chemical composition. The bio-oils contain a large number
N-ethylpyrrolidine, 1,5-dimethyl-2-pyrolidinone, caprolactam
of different compounds, making complete chemical characteriza-
and indole (Table 6). The majority of nitrogenous compounds in
tion of them very difficult. Chemical composition of HTL bio-oils
bio-oil can be supported by the existence of aliphatic protons
were analyzed with GC-MS, 1H NMR, and FTIR spectroscopic
a-to heteroatom or unsaturation and aromatic-heteroaromatic
techniques. In the FTIR spectrum of HTL-275 bio-oil, given in
protons as revealed by 1H NMR spectroscopy analysis. Besides
Supplementary 2, there are indications of peaks at 3199 and
nitrogenous compounds, aromatic compounds such as benzene
3017 cm
1 which can be assigned to aromatic CAH stretching
derivatives, phenols and derivatives, multi-ring heterocyclic
and CAH stretching vibrations of N-heterocyclics such as pyridines,
compounds and oxygenated heterocyclic compounds were also
quinolines, and pyrimidines. Intensive bands were observed at
identified. Given the high nitrogen content of bio-oils, it is not
2920 cm
1and 1673 cm
1, and assigned to aliphatic CAH
surprising that the nitrogenous heterocyclic and aliphatic com-
stretching and aromatic C@C stretching vibrations of amide 1,
pounds formed the majority of bio-oil. Kruse et al. (2005, 2007)
respectively. In addition, the bands observed at 1554 cm
1 and
stated for biomass composed of carbohydrates together with
1455 cm
1 were assigned to secondary acyclic amides and CAN
proteins that glucose or its consecutive degradation products react
stretch of primary amides, respectively, while the bands at 950–
with amino acids or its consecutive degradation products via the
700 cm
1 were assigned to aromatic CAH bending vibration (Xiu
Maillard reaction to form nitrogen containing cyclic organic
et al., 2010; Schnitzer et al., 2007).
Recently, NMR spectroscopy has also been utilized to determine
Table 6
some characteristics of bio-oils, such as presence of functional Main compounds in bio-oils (relative area, %).
groups, degrees of branching or saturation, aromatic content. The
Compound HTL-275 HTL-325
percentages of protons based on 1H NMR spectroscopy analysis
of bio-oils grouped according to chemical shift range proposed 3-Methyl-1-butanamine – 1.13
2,2-Dimethoxybutane 1.05 –
by Mullen et al. (2009) are given in Table 5. The most upfield region
1-Methyl piperidine – 0.96
of the spectra, from 0.5 to 1.5 ppm, represents aliphatic protons N-Ethylpyrrolidine 3.18 –
that are attached to carbon atoms at least two bonds removed from 1-Ethyl piperidine 1.32 –
a C@C double bond or heteroatom (O or N). This region was the 2-Pyridinone – 1.26
most populated (60% of all protons) for both HTL-275 and HTL- 4-Methyl pyrimidine 0.35 –
Ethylbenzene – 0.88
325 indicating their higher aliphatic content. The integrated region
Pyrrole 0.25 0.41
from 1.5 to 3.0 ppm represents protons on aliphatic carbon atoms Styrene 0.51 1.63
that may be bonded to a C@C double bond (aromatic or olefinic) or Benzenethiol 0.38 –
are two bonds away from a heteroatom. Both bio-oils again had 2-Ethylpiperidine 6.16 2.14
high levels of protons in this spectral region (25–27%). According 1-(3-Aminopropyl)-2-pipecoline 0.84 –
1H-Pyrrole, 3-ethyl-2,4-dimethyl- 0.95 1.3
to Mullen et al. (2009), high amount of protons in the region both Acetamide, N-ethyl-(CAS) 1.14 0.85
from 0.5 to 1.5 ppm and 1.5 to 3.0 ppm describes the evidence that 1,3-Dioxane 1.11 –
bio-oil has high calorific value. 1H-Pyrrole, 1-pentyl- 1.23 1.89
The region of the spectrum, from 3.0 to 4.4 ppm, could N-ethyl-propanamide 0.59 0.68
Guanosine, 20 -deoxy- 0.32 –
represent protons on carbon atoms next to an aliphatic alcohol
Benzeneethanamine 1.53 2.51
or ether, or a methylene group that joins two aromatic rings and N-methyl-propanamide – 0.7
contains 4–6% of the protons in the bio-oil. The region between Phenol 1.38 –
4.4 and 6.0 ppm represents aromatic ether protons (i.e., lignin 3-methyl-butanamide, 1.29 –
derived methoxyphenols). The aromatic region of the spectrum 2-Amino-5-nitropyridine 0.64 –
trans-2-Methoxy-6-(formylmethyl)tetrahydropyran 6.25 8.96
(6.0–8.5 ppm) contains between 3% and 4% of the protons in the 3-Methyl-N-ethylsuccimide 1.15 –
N-butylidene-1-butanamine 1.39 0.78
4-methyl-pentanamide, 0.55 –
Table 5 p-Hydroxyphenyl-phosphonicacid – 1.42
Percentages of protons based on 1H NMR analysis of bio-oils grouped according to N-(3-methylbutyl) acetamide 1.71 2.14
chemical shift range. 1-Methyl-2-pyrrolidinone – 2.19
Pyrrolidine, 1-acetyl- 1.77 2.02
Proton type d (ppm)a HTL-275 HTL-325
1,5-Dimethyl-2-pyrrolidinone – 2.76
Aromatic-heteroaromatic 6.0–8.5 3.2 4.1 Phenol, 4-ethyl- 0.38 1.28
Methoxy, carbohydrates 4.4–6.0 3.7 3.3 2-Piperidinone 6.17 6.28
Alcohols, methylene, dibenzene 3.0–4.4 4.2 6.1 N,N-Bis(2-hydroxyethyl)-2-aminoethanesulfonic acid 1.82 1.19
Aliphatics a-to heteroatom or unsaturation 1.5–3.0 25.6 26.5 Caprolactam 3.52 1.93
Alkanes 0.5–1.5 63.3 60.1 Methotrexate 0.61 0.57
a
Oxacyclododecan-2-one 0.46 1.00
The percentages of protons grouped according to chemical shift range proposed
Indole 2.02 1.84
by Mullen et al. (2009).
538 I.C. Kantarli et al. / Waste Management 56 (2016) 530–539
compounds. These types of compounds are referred to strong free
radical scavengers and inhibit free radical chain reactions. Inhibi-
tion of these reactions reduces the formation of gases with a corre-
sponding increase in the DOC value, since gases are formed mainly
by free radical reactions (Kruse et al., 2007).
3.4.3. Composition of gas products
Main component of gaseous products from all HTL experiments
was CO2 and this indicates that hydrothermal conversion proceeds
through decarboxylation. One might think that main gas product
from thermal degradation of proteins is ammonia. However, since
NH3 gas is readily dissolved in aqueous reaction solution, determi-
nation of it in the gas products was not possible. The high pH value
(8–9) of aqueous solution also supports that NH3 was dissolved in
aqueous solution. The composition of gaseous product showed lit-
tle change with the temperature. The mole percent of CO2, CO and
H2 in gas products were in the range of 88.7–97.9%, 0–2.7% and
1.7–6.4%, respectively.
4. Conclusion
Poultry litter was subjected to hydrothermal carbonization and
pyrolysis in order to convert it to the energy-value solid product,
biochar. Hydrothermal carbonization was proved to be more suc-
cessful at energy densification, while higher energy yield was
obtained by pyrolysis. Biochar obtained by hydrothermal car-
bonization at reaction temperatures higher than 200 °C was com-
parable to lignite, while that obtained by pyrolysis at reaction
temperatures higher than 250 °C was comparable to bituminous
coal. Because of high nitrogen content, biochar has to be blended
with a low nitrogen content fuel for combustion process. On the
other hand, based on the results of preliminary studies, poultry
meal was preferably subjected to hydrothermal liquefaction in
order to convert it to the energy-value liquid product, bio-oil.
Hydrothermal liquefaction of poultry meal produced bio-oil having
considerably high calorific value with a yield of 35 wt.%, but the
quality of bio-oil was found to be poor due to its nitrogenous hete-
rocyclic and aliphatic content. Therefore, bio-oil requires further
upgrading in order to utilize it as a transport and heating fuel. In
conclusion, poultry wastes can be considered as potential feed-
stocks to obtain biochar and bio-oil and utilized for energy recov-
ery by hydrothermal processes, besides gasification.
Acknowledgements
We would like to thank TUBITAK for financial support by BIDEB
2209-A National/International Research Projects Supporting Pro-
gram for University Students.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.wasman.2016.07.
019.
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