Fuel 183 (2016) 366–372

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Preparation and characterization of agricultural waste biomass based

hydrochars
Yusuf Osman Donar, Ezgi Çağlar, Ali Sınağ ⇑
Ankara University, Department of Chemistry, 06100 Besßevler, Ankara, Turkey

h i g h l i g h t s

 Carbon content increased with increasing temperature.

 Prepared hydrochars contain hydroxyl, carbonyl, carboxyl, ether and ester groups.
 Spherical/semi-spherical particles were prepared.
 Semi-graphitized amorphous carbonaceous structure formed.

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

Article history: In this study hazelnut shell and olive residue were hydrothermally carbonized in a stainless steel auto-
Received 29 October 2015 clave. Chemical, structural and physicochemical properties of obtained hydrochars were investigated in
Received in revised form 29 April 2016 dependence of the reaction parameters and characterized by use of various techniques. Reaction temper-
Accepted 22 June 2016
ature was found to have a much stronger influence on hydrothermal carbonization (HTC) of biomass than
Available online 27 June 2016
reaction time after 2 h. Hydrochar samples consist of spherical/semi-spherical particles in nano to micron
size with aromatic framework. Hazelnut shell based hydrochars have higher number of O-containing
Keywords:
reactive functional groups compared with the olive residue based hydrochars. Because of the knowledge
Hydrothermal carbonization
Waste biomass
gaps in hydrochar characterization, more comprehensive product characterization and reporting are
Carbonaceous spheres needed to advance our understanding of HTC processes, products and applications. By the help of the
Surface functionalities results of this study, it will be possible to choose the appropriate hydrochar characteristics in various
applications of hydrochars.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction Another advantage of the hydrothermal method is to allow car-

Carbonaceous materials received a great attention in the last
decade because of their wide range of applications such as water
purification [1], or as electrode materials for super-capacitors [2],
catalysts [3–5], catalyst support material [6] and solid fuel [7,8].
The hydrothermal carbonization (HTC) process is one of the most
common thermochemical conversion technologies which first
was demonstrated in 1913 [9] and has practiced extensively after
2000. At hydrothermal conditions biomass is converted to car-
bonaceous materials in water, under mild thermal conditions
(150–350 °C), autogenous pressure and with relatively short reac-
tion times [10].
⇑ Corresponding author.
E-mail address: sinag@science.ankara.edu.tr (A. Sınağ).
bonaceous sphere formation of nano and/or micro size. This car-
bonaceous spheres have a wide variety of surface functional
groups such as AOH, AC@O and ACOOH. Hydrothermal carboniza-
tion of biomass in aqueous media allows lots of oxygenated func-
tional groups to occur on the surface of the carbonaceous material
and these functional groups play a very critical role for some appli-
cations such as for dyes or heavy metal ion adsorption [11,12].
Generation of carbonaceous materials from waste biomasses as
carbon sources has a critical importance since it is a renewable and
environmentally benign method. The biomass feedstocks used in
this work were hazelnut shell and olive husk. Hazelnut shell is
an important agricultural residue in Turkey being the largest hazel-
nut producer in the world [13]. Olive residue is also an important
biomass generated especially in the Mediterranean region of Tur-
key as a byproduct of olive oil production.

http://dx.doi.org/10.1016/j.fuel.2016.06.108
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.
 Y.O. Donar et al. / Fuel 183 (2016) 366–372
In our previous work low temperature (180 °C) hydrothermal
carbonization of saccharides and waste biomasses were success-
fully performed and evaluated in terms of the char formation
mechanism [7]. In the present paper, the effects of operational con-
ditions on the chemical, morphological and structural characteris-
tics of hydrochars obtained from the two bio-residues were
investigated. Even though the hydrothermal carbonization of bio-
mass has been investigated by various workers [14,15], this work
differs from those in regard to the use of wide variety of analysis
techniques to improve the understanding of operation conditions
on the chemical, structural, physicochemical properties and forma-
tion process of hydrochars.
2. Materials and methods
2.1. Materials
Hazelnut shell (HS) and olive residue (OR) were used as car-
bonaceous material precursors. Olive oil waste was provided from
a local olive oil factory at Muğla from Turkey and formed the
remaining material after the oil extraction from the olive kernel.
Hazelnut shell was supplied from the Black sea region in the north-
ern part of Turkey. The proximate and ultimate analysis of the raw
biomass samples (HS and OR) are given in Table S1 in supporting
information (SI). The air dried biomasses were milled and then
sieved through a 425 lm mesh.
2.2. Hydrothermal carbonization experiments
The hydrothermal carbonization experiments were carried out
in, a 1 L stirred pressure reactor (Parr, model 4571) under different
reaction conditions changing the temperature (180, 220 and
260 °C) and the reaction time (2, 4 and 6 h). In a typical run, 40 g
biomass was dispersed in 400 mL distilled water in the reactor
and heated with 4 °C/min. It took about 45, 60 and 75 min to reach
180, 220 and 260 °C temperatures, respectively. After reaction
solid product was separated from liquid via vacuum filtration.
The carbonaceous material was washed with distilled water 3
times and dried in an oven at 80 °C for 24 h. The obtained hydro-
chars from hazelnut shell (HS) and olive residue (OR) were labeled
according to biomass type, reaction temperature and reaction time
Fig. 1. Effects of reaction parameters on the solid product yield, (a) 4 h and (b) 220 °C.
367
respectively. For instance, HTC-OR (260 °C, 4 h) refers to
hydrothermally carbonized olive residue at 260 °C for 4 h.
2.3. Analysis of hydrochars
X-ray Diffraction analyses of biomass and hydrochar samples
were carried out by a Rigaku D/Max 2200ULTIMAN X-ray diffrac-
tometer, using CuKa radiation. Elemental analysis of hydrochars
and biomass were determined using a LECO 932 CHNS elemental
analyzer. XPS spectra was recorded by a PHI-5000 Versaprobe
using Al monochromatic X-ray anode and Gaussian peaks for the
peak fitting. 13C CP-MAS NMR analyses were conducted by a Bru-
ker Avance 300 MHz (7T) spectrometer spinning at MAS rate
nMAS = 7 kHz. Raman spectra were obtained from a Horiva (Lab-
Ram HR-800) analyzer with 532 nm laser in the range of 1000–
2000 cm 1. High resolution transmission electron microscope
(CTEM) analysis was performed with an FEI Tecnai G2 (at
200 kV) transmission electron microscope to determine the parti-
cle size and shape of the hydrochar particles. Scanning electron
microscope (SEM) images were obtained using a QUANTA 400F
Field Emission SEM device.
3. Results and discussion
3.1. Recovered hydrochars yield
The effects of reaction parameters on the solid product yield are
shown in Fig. 1. High carbonization rates lead to formation of gas-
eous and liquid products and solid product yield decreased with
the separation of this by-products when compared with the initial
weight of biomass. Hydrothermal carbonization of waste biomass
may occur at 180 °C [7], even though cellulose and lignin do not
undergo any significant changes below 220 °C temperature. It
can be explained by the thermally unstable hemicellulose content
of the lignocellulosic biomass (Table S1 in SI). At 180 °C, olive resi-
due has a low solid product yield (high conversion rate) compared
with hazelnut shell because of the higher hemicellulose content
relative to hazelnut shell. Low concentrations have provided better
carbonization for waste biomasses.
368 Y.O. Donar et al. / Fuel 183 (2016) 366–372

3.2. Chemical analysis of hydrochars

The Elemental analysis regarding C, H, O and N results (Fig. 2)

show that the carbon content of hydrochar samples increased with
increasing temperature. This result indicates that carbonization
process is positively influenced by reaction temperature; on the
other hand, different reaction times showed no significant effects
on the elemental composition of hydrochar samples.
Regarding the H/C and O/C ratios is useful to characterize the
chemical transformations that take place during the hydrothermal
carbonization of input materials [16]. Decreasing of H/C and O/C
ratios indicate ACH3 and CO2 elimination respectively. High O/C
ratio is the evidence of low carbonization rates and the existence
of polar functional groups on the hydrochars [17]. H/C and O/C
ratios of hydrochars show that (Fig. 3) olive residue based hydro-
chars have a higher carbonization rate than hazelnut shell based
hydrochars and hazelnut shell based hydrochars have higher num-
ber of O-containing reactive functional groups at high reaction
temperatures compared with the olive residue based hydrochars
because of the high O/C ratio. Fig. 3. Atomic H/C–O/C ratios of raw biomasses and synthesized hydrochar
Hydrochars obtained at 180 °C and 220 °C show two XRD peaks samples.
around 15° and 22° and these peaks correspond to amorphous cel-
lulose structure [18]. It is interesting that when the crystal struc-
ture of pristine cellulose decomposes at 220 °C [19],
characteristic cellulose peaks are still observed at this temperature 3.3. Structural analysis of hydrochars
in waste biomasses (Fig. S1 in SI). This could be the result of the
complex structure of waste biomasses. Biomass has three major Table 1 shows the Raman spectra information on hydrochar
components; cellulose (40–60%), hemicellulose (20–40%) and lig- samples. The signal obtained in the low frequency region shows
nin (10–25%) [20]. Lignin is the most robust component among two specific bands for carbonaceous materials; the graphite (G)
these structures and it acts as a protective layer [21]. Because of band between 1570 cm 1 and 1600 cm 1 and the disorder-
the protective lignin layer, the crystalline structure of cellulose is induced (D) band between 1330 cm 1 and 1360 cm 1 [22]. The G
preserved at 220 °C in the waste biomasses but when the temper- band is associated with the in-plane bond-stretching motion of
ature was raised to 260 °C, no crystalline peaks of cellulose were pairs of sp2 carbon atoms in aromatic and olefinic molecules and
observed anymore and a new sharp peak appeared at 26.5°, which the D band is assigned to ring breathing vibrations in condensed
corresponds to 002 lattice spacing indicating graphitic structure benzene rings in partially hydrogenated amorphous carbon
and p-p⁄ transitions [22]. Consequently, semi-graphitized amor- materials [16]. Characteristic D and G bands were observed for
phous hydrochar was prepared at 260 °C using the waste bio- all prepared hydrochar samples. The graphitization degree of car-
masses as a carbon source. bons can be calculated by the width of the IG peak and the ID/IG

Fig. 2. Elemental composition of prepared hydrochars.

 Y.O. Donar et al. / Fuel 183 (2016) 366–372
Table 1
Raman spectra information on hydrochar samples.
Sample ID ID IG
HTC-HS (260 °C, 4 h) 5246.66 9171.01
HTC-HS (180 °C, 4 h) 1759.16 2848.4
HTC-OR (180 °C, 4 h) 6618.48 9782.54
HTC-OR (260 °C, 4 h) 15045.99 23783.71
ratio. A bigger ID/IG ratio indicates a lower graphitization degree
[2]. The calculated ID/IG values of hydrochars are shown in Table 1.
The graphitization degree of the other hydrochar samples range
from 0.57 to 0.68 indicating the amorphous carbon structure with
a large amount of lattice edges (defects) in plane terminations of
disordered graphite of carbonaceous materials [23].
13
C CP-MAS NMR analyses provide reliable structural informa-
tion about cellulose, lignin, coals and different types of carbon-
based materials as well as hydrothermal carbons [24]. 13C CP-
MAS NMR spectra of hydrochars obtained at different tempera-
tures are given in Fig. 4. The peaks which belong to unconverted
cellulose are still observed at hydrochar obtained at from low tem-
peratures (180 °C) but when temperature was raised to 260 °C, no
peaks were observed in relation to unconverted cellulose (Table S2
in SI). The intensity of the peak which indicates monocyclic/poly-
cyclic aromatic carbon of hydrochar is increased with decreasing
furanic structure peak intensity as a result of aromatization
reactions.
Hydrochar has large amounts of functional groups on the outer
layers and these functionalities were determined with X-ray pho-
toelectron spectroscopy (XPS). C1s core level spectra of raw bio-
mass and hydrochars obtained from the two bio-residues are
13
Fig. 4. C CP-MAS NMR spectra of hydrochars.
369
1 1
cm (D band) cm (G band) ID/IG
1380.69 1581.03 0.57
1378.36 1586.93 0.62
1368.38 1578.86 0.68
1388.52 1588.66 0.63
given in Fig. 5. As a result of peak correction, five signals were iden-
tified at 284.6 ± 0.2 eV (C1), 285.7 ± 0.2 eV (C2), 287.3 ± 0.2 eV (C3),
289.1 ± 0.2 eV (C4) and 291.1 ± 0.2 eV (C5). These peaks corre-
spond to carbon group (C@C, CHx, CAC), hydroxyl groups or ethers
(ACAOR), carbonyl or quinone groups (˜C@O), and carboxylic
groups, esters, or lactones (@COOR) and p-p⁄ transitions, respec-
tively [16,25]. The first four functional groups generated from
aromatization, dehydration, condensation, and esterification reac-
tions respectively during hydrothermal carbonization process
[23]. The last one is the reason of condensate aromatic structure
formation. All other hydrochar samples have p-p* transitions
owing to condensate aromatic structure.
Hydrochar samples and biomass feedstock were analyzed semi-
quantitatively with the XPS analysis according to fitted peak areas
(Fig. S2 in SI) [26]. No peaks belonging to C5 groups were observed
in the hazelnut shells and olive residue. When they were
hydrothermally carbonized C5 group appeared at. The peak area
of C5 groups of olive residue based hydrochar increased with
increasing reaction temperature contrary to hazelnut shell based
hydrochars. The presence of carbonyl/carbonate groups (C3) is also
important for many applications [26]. The maximum C3 peak area
for hazelnut shell and olive residue is obtained at 180 and 220 °C,
370 Y.O. Donar et al. / Fuel 183 (2016) 366–372

Fig. 5. XPS spectra of biomass and hydrochar (4 h).

respectively. When temperature was raised to 260 °C, C3 peak area
can decrease because of the decarboxylation reactions, which is
consistent with the C/H and C/O considerations.
3.4. Physicochemical analysis and mechanistic consideration of
hydrochar formation
SEM and TEM images of hydrochar samples obtained from the
two biomass types are given in Fig. 6. Hydrothermal carbonization
of biomass is a complex process due to its complex structure which
consists of cellulose, hemicellulose and lignin. Thermal stability of
these constituents is ranked as follows: hemicellulose < cellu-
lose < lignin [20]. Hemicellulose is the least stable part of lignocel-
lulosic biomass and hydrolyzed furfural like components are
responsible for sphere formation at low temperatures. Hazelnut
shell and olive residue have different hemicellulose, cellulose and
lignin contents (Table S1). High hemicellulose content improves
sphere formation and this phenomenon is proved with SEM images
of olive residue based hydrochars (Fig. 6). Olive residue contain
more spherical particles compared to hazelnut shell. In spite of
the fact that cellulose and lignin need higher temperatures
(P220 °C) to decompose, hazelnut shell and olive residue are dis-
integrated at low temperatures (180 °C) as examined in the previ-
ous work [7]. These observations support that the first step of
hydrothermal carbonization of waste biomass is hemicellulose
degradation which is the reason of the sphere formation. After that,
cellulose and lignin decompose respectively to form condensed
aromatic structure with increasing temperature. This observation
is also consistent with the results obtained from semi-
quantitative XPS analysis.
 Y.O. Donar et al. / Fuel 183 (2016) 366–372
Fig. 6. SEM and TEM images of hydrochars (260 °C, 4 h).
4. Conclusions
Hydrochars were successfully prepared from waste biomass
and the effects of different reaction conditions on the hydrochar
production and properties were identified. Hydrochars obtained
under different hydrothermal conditions will have different chem-
ical and physical features because different reaction conditions
alter the thermodynamics and kinetics of the hydrothermal car-
bonization reaction. Reaction temperature is the main parameter
for the hydrochar preparation; however, reaction time has a slight
influence. All hydrochar samples have aromatic structure and large
amounts of O-functionalities on the surface. The resulting hydro-
char consists of micron/submicron size spherical and semi-
spherical particles, which are formed by the polymerization of fur-
fural species. From practical point of view, there is a number of bio-
mass feedstocks which can be converted into hydrochar using HTC
process. In addition, the HTC process can be further improved and
scaled up by investigating other factors of HTC like temperature
and reaction time. Short reaction times adequate to large scale pro-
duction at high temperatures with regards to energy saving. How-
ever further investigations about reaction kinetics study and
exergy analysis could be useful to obtain its maximum perfor-
mance. To do this, better reporting and standardization of hydro-
char characteristics and production conditions are required as
the characteristics of hydrochar depend highly on feedstock and
process conditions.
371
Acknowledgement
The authors would like to acknowledge TUBITAK (The Scientific
and Technological Research Council of Turkey) for providing finan-
cial support for this work through the Project ‘‘113Z635”.
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.fuel.2016.06.108.
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