Accepted Manuscript

Hydrothermal carbonization, torrefaction and slow pyrolysis of miscanthus

giganteus

Małgorzata Wilk, Aneta Magdziarz

PII: S0360-5442(17)30389-4

DOI: 10.1016/j.energy.2017.03.031

Reference: EGY 10498

To appear in: Energy

Received Date: 16 December 2016

Revised Date: 27 February 2017

Accepted Date: 07 March 2017

Please cite this article as: Małgorzata Wilk, Aneta Magdziarz, Hydrothermal carbonization,
torrefaction and slow pyrolysis of miscanthus giganteus, Energy (2017), doi: 10.1016/j.energy.
2017.03.031

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 ACCEPTED MANUSCRIPT

 The pre-treatment processes of Miscanthus x Giganteus were investigated.

 The effect of temperature and residence time on hydrothermal carbonization,
torrefaction and slow pyrolysis was studied.
 The physical and chemical properties of raw, hydrochars, torrefied Miscanthus and
pyrochars were determined.
 The thermal behaviour of raw and pretreated Miscanthus was investigated by TGA
analysis.
 ACCEPTED MANUSCRIPT
HYDROTHERMAL CARBONIZATION, TORREFACTION AND SLOW
PYROLYSIS OF MISCANTHUS GIGANTEUS

Małgorzata WILK*, Aneta MAGDZIARZ

AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow, Poland
e-mails: mwilk@agh.edu.pl, amagdzia@agh.edu.pl
* corresponding author: mwilk@agh.edu.pl
phone no: +48126173198

Abstract
The main aim of the paper is to analyze the effect of different pretreatment processes (HTC,
torrefaction and slow pyrolysis) on the properties of Miscanthus Giganteus. In this study, the HTC
process was conducted in a Zipperclave Stirred Reactor under following parameters: temperature
(180, 200 and 220 C), pressure (< 2.5 MPa) and residence time (2, 3, 4, 6, and 12 h). The effect of
temperature and residence time of torrefaction and slow pyrolysis were studied in specially
designed laboratory apparatus. Torrefaction temperature was held at 230, 260, and 290 °C, and
residence time was specified for 0.5, 1.0 and 1.5 h. The preliminary study for slow pyrolysis
processes were performed at 350, 400, 450 and 500 C for 0.5, 1.0 and 1.5 h. The thermal behaviour
of raw and pretreated Miscanthus was investigated by TGA analysis. Finally, HTC, torrefaction and
slow pyrolysis processes proved an improvement in the combustible characteristics of the obtained
biochars compared to raw biomass by the spectacular increase of carbon content 36%, 34% and
80%, respectively.

Keywords: hydrothermal carbonization, torrefaction, slow pyrolysis, Miscanthus Giganteus

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1 Introduction

Currently, biomass is one of the most promising, renewable alternative for fossil fuels.
Biomass is mainly derived from wood and wood processing waste, plants derived from energy
crops, agricultural products and organic waste. Nowadays, biomass energy crops have got a lot of
interest because of their rapid growth, low mineral content, high biomass yield and good carbon
balance [1]. The most famous energy crops are willow or switch grass, but Miscanthus is also well
known because of its wide availability and good combustible properties. It is a woody, perennial
and rhizomatous grass [2,3] which has great energy potential. In order to obtain energy from
biomass, the combustion of biomass in energy units has already been conducted [4-6], but there are
some operating difficulties which need to be solved. Miscanthus, as with all kinds of biomass, has
the same disadvantages, for example, moisture content, ease of biological degradation, low bulk
density, low energy density, nonhomogeneous chemical properties, and the milling of raw, wet
biomass [7]. Therefore, the operating problems include: high cost of transportation, complications
with storage, low efficiency of thermal processes, and limitation of its utilization. That is why a
special pretreatment of feedstock is required to enhance their combustible properties (Fig. 1).

Fig. 1. The route of biomass to energy production.

There are several thermal technologies for utilizing biomass to obtain useful forms of energy
through the correct pretreatment. Additionally, there are different methods of pretreatment which
are used to improve the character of biomass, such as dewatering, drying and pelletization [8].
Nevertheless, some difficulties can be found within these processes concerning raw biomass
properties. For example, the pelletization process does not eliminate the main weak point of raw
biomass: its hydrophilic character and ease of biological degradation. Promising options are
hydrothermal carbonization, torrefaction, and slow pyrolysis processes, which are effective ways to
densify the energy content of biomass. Additionally, it helps to reduce transportation and storage
problems during handling biomass in large quantity. Hydrothermal carbonization (HTC) is a
thermochemical process which involves the application of heat and pressure to convert raw material
in the presence of water into carbonaceous biofuel. The HTC process results in three types of
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products: gases, aqueous chemicals, and a solid hydrochar. The gas product is approximately 1-3%
of the raw material, consisting mainly of CO2. The aqueous extractive compounds can easily be
filtered from the reaction solution, avoiding complicated drying schemes and costly isolation
procedures. They are primarily inorganic salts, sugars, and organic acids. Hydrochar is a
homogenized, carbon-rich, and energy-dense solid fuel, which is biologically sterilized due to
thermal treatment. The mechanisms of hydrothermal carbonization are associated with a series of
hydrolysis, condensation, decarboxylation, and dehydration reactions. Reaction temperatures are
applied within a range of 180-230 C and the various pressures are maintained above the saturation
pressure to ensure the liquid state of water. The HTC method has generally been used for a wide
range of biomass feedstock where the effect of temperature, residence (carbonization) time, and
carbonization yields have been studied [9-13]. Torrefaction is a process where raw biomass is
heated under an inert atmosphere within a temperature range of 200–300 C and where the hydroxyl
groups are removed, thus producing hydrophobic material [14-21]. Whereas, slow pyrolysis is the
thermal decomposition of biomass occurring in the absence of oxygen within a temperature range of
350-700 °C with a heating rate of 0.1-1 K/s [22-26].
Although, Miscanthus has been chosen previously for research in energy production because it
grows quickly and it is easy to maintain [27], there are few papers concerning carbonization of this
crop. Hydrothermal carbonization, torrefaction and slow pyrolysis of Miscanthus were also
conducted to find out the effect of these processes on the combustion behaviour of hydrochar,
torrefied material, and pyrochar [28-31]. Torrefied Miscanthus has been studied in the terms of
residence time and temperature on its composition, grindability and usefulness towards pyrolysis
and gasification versus raw material [32]. The ash behaviour, obtained in these processes, was also
studied in terms of the properties of the fuel and conditions of the processes [33,34]. Additionally,
the sorptive and fertile characteristics of the obtained carbonized solid products were studied in
respect of its potential as a carbon sequesterer, and soil fertility enhancer [24,35-37]. Although, the
above mentioned pretreatment processes were studied, therefore the detailed description is not
sufficiently known and they will also be under discussion in this work.
The objectives of this study were to investigate the impact of residence time and temperature
on the properties of Miscanthus by HTC, torrefaction and slow pyrolysis processes. Thus, the
characterization of the biomass, before and after the carbonization processes is presented with
respect to their chemical composition and their physical properties.

2 Materials and methods

2.1 Materials

The biomass feedstock, Miscanthus Giganteus (named Miscanthus) used in this study was
supplied by ECOPROD Ltd from the agricultural area of Silesia in Poland. The sample was
delivered as pruning straw and had to be chopped and grinded using a cutting mill. It was then
sieved to obtain a particle size range between 0.75 and 1.02 mm for further investigation. Samples
were used as required for the HTC, torrefaction and slow pyrolysis processes.

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2.2 Methods

2.2.1 HTC experiments

HTC was performed in a stainless steel, Zipperclave Stirred Reactor with a reactor volume of
1000 ml, and equipped with a MagneDrive Agitator (Parker Autoclave Engineers). The control
panel provides a programme which regulates the heater temperature and mixer speed. A detailed
description of the HTC apparatus is presented in [9]. An HTC apparatus is shown in Fig. 2.

Fig. 2. The HTC apparatus [9].

1-burette, 2-valve, 3-pressure gauge, 4-thermocouple, 5-electrical furnace, 6-cooling coil, 7-stirrer, 8-cooling jacket.

For each run, 50 g of raw Miscanthus was dispersed in 500 ml of de-ionized water and placed
into the vessel. The mixer was stirred continuously at 150 rpm to ensure uniformity of the reaction
temperature in the samples. The reactor was then sealed and heated up to 200 C in an electric
furnace. When this temperature was reached, the following carbonization times-2, 3, 4, 6 and 12 h-
were maintained. The various pressures were stabilized. Additionally, in order to investigate of the
temperature impact, runs at180 and 220 C for 4 h, as well as pressure at 1.5 and 2 MPa were
carried out. For all cases the procedure was as follows: at the end of the carbonization time, the
heater was turned off and the reactor was taken from the furnace and cooled down by water via a
cooling coil. When the pressure and temperature decreased to room temperature, the gaseous phase
was trapped in a Tedlar bag, and then the reactor was opened to collect the remaining products. The
mixture of solid and liquid products was firstly extracted from the vessel and placed in a graduated
cylinder for observation of the sedimentation time. Then, the solid product was separated from the
liquid phase by using a vacuum filtration apparatus through microfiltration filter paper and oven
dried at 105C for one day. The liquid phase and hydrochars were weighed and stored in sealed
containers until further analysis was carried out.

2.2.2 Torrefaction and slow pyrolysis experiments

Torrefaction and slow pyrolysis are two related processes in which Miscanthus is heated in an
oxygen-free environment. The difference between the two processes is that torrefaction employs
milder temperatures of 200–300 °C in comparison to slow pyrolysis 350–700 °C, when conducted
at low heating rates. The scheme for the torrefaction set-up specially designed for that purpose is
shown in Fig. 3 and discussed in detail in [15]. Both processes were carried out with the same
apparatus.

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Fig. 3. Schematic diagram of torrefaction set-up [15].

The experimental apparatus consists of a quartz tube reactor (500 mm in length and with a
diameter of 40 mm) equipped with a temperature control system, an argon gas tank, a rotameter and
a product gas treatment unit. The experimental investigation of the torrefaction process was
performed using 2 g of Miscanthus placed in the ceramic rectangular crucible in the middle of a
quartz tube reactor. Torrefaction temperature was held at 230, 260, and 290 °C, and residence time
was specified for 0.5, 1.0 and 1.5 h time, respectively. Then, a constant 2.5 l/min flow rate of argon
was passed through the reactor to keep the inert atmosphere inside. This allowed the removal of
and, alternatively, trapping in a gas bag of the torgas. At the end of the fixed time period, the
crucible was removed from the tube reactor, cooled down and weighed to determine the torrefaction
yield. Thereafter, the torrefied samples were further analyzed to characterize their physical and
chemical properties. To ensure measurement quality for the results the experiment, under all of the
studied conditions, was repeated.
The same procedure was adapted for the preliminary study of slow pyrolysis. In this case the
pyrolysis temperature was held at 350, 400, 450 and 500 °C, and the same range of residence time
was specified. The obtained pyrochars were analyzed taking into account the carbon content.
It is worth to mention that presented experimental work, design and construction of
pretreatment units required research involvement and time to obtain final experimental conditions.

2.2.3 Product characteristics

The proximate and ultimate analyzes of Miscanthus and the solid products from hydrothermal
carbonization, torrefaction and slow pyrolysis were performed according to European Standards
(Table 1). The samples obtained under hydrothermal carbonization were named HTC_2, HTC_3,
HTC_4, HTC_6, and HTC_12, respectively, according to the carbonization times used during the
process. The torrefied Miscanthus samples were named TM_230, TM_260, TM_290 and the
pyrochar samples were named SPM_350, SPM_400, SPM_450, SMP_500 according to torrefaction
and slow pyrolysis temperatures.
The moisture content was determined by maintaining 1 g of the samples in the drying system at
105 C to a constant mass according to EN 15934:2012. The ash content was determined by
burning a 1 g sample of all studied solid recovered fuels in a muffle furnace at 250 +/- 10 C for 50
min and then at 550 +/- 10 C for 4 h, according to the EN 15403:2011 European Standard. The
volatile matter was determined by maintaining the 1g mass samples at 900 +/- 10 C for 7 min
using the EN 15402:2011 method. The fixed carbon was determined by difference. The ultimate
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analysis (carbon, hydrogen and nitrogen content) was measured by Elemental Analyzer Truespec
CHN Leco. The LECO CHN628 is a combustion elemental C, H, and N instrument that utilizes
only pure oxygen in a furnace, ensuring complete combustion and superior recovery of the elements
of interest. An Analyzer CHS580 ELTRA was used to determine sulphur content. The analyzer is
designed to determine the carbon and sulphur content in a wide variety of organic materials as well
as some inorganic materials by combustion with non-dispersive infrared detection.
The higher heating values of raw and pretreated solid samples from HTC were determined
using a KL-10 bomb calorimeter. In the case of torrefaction and slow pyrolysis the HHV were
calculated according to the Friedl equation [38], namely:

HHV = 3.55 ∙ C2 - 232 ∙ C - 2230 ∙ H + 51.2 ∙ C ∙ H + 131 ∙ N + 20600, kJ/kg (1)

Based on ultimate analyzes the fuel and atomic ratios were found. The ultimate and proximate
analysis, and also the HHV, H/C, O/C, mass, energy, ash yields, and energy densifications ratios are
summarized in Table 1, 2 and 3.
The energy densification ratio formula is expressed as:

Energy density ratio = HHV pretreated Miscanthus/HHV raw Miscanthus (2)

The selected gaseous phases from HTC, collected in Tedlar bags, were tested by Gas
Chromatography using Agilent 7890A GC.
After filtration of the solid, dark brown product from the liquid phase of HTC experiments, the
HTC-water was still a dark yellow colour. In the order of carbon determination 100 cm3 of HTC-
water was distilled under lower pressure. The obtained 90% of distillate was clear and transparent,
while the other 10%, was dark brown. This was heated up in a water bath to evaporate. The
remaining dark, solid product was dried at 105C, weighed and then analyzed in terms of its carbon
content due to carbon balance. The chemical analyzes of the selected samples of HTC-water was
carried out using the liquid chromatography method. COD (Chemical Oxygen Demand) was also
performed, but only for three representative samples, 4 h and 180 C, 12 h and 200 C, and 4 h and
220 C, using potassium dichromate. Finally, pH, conductivity, and oxygen demands for both HTC-
water and distillate samples were measured by Multifunction Laboratory Meter CX-505
ELMETRON (Table 4). Additionally, an acid-base titration of the distillate was carried out to
determine the concentration of acetic acid.

2.2.4 TGA method

The combustion process of Miscanthus and hydrochars was studied by thermogravimetric

analysis in air atmosphere (40 ml/min), at a constant heating rate of 10 /min by Netzsch STA 449
F3 Jupiter. The samples were heated in alumina crucibles from an ambient temperature up to
700 C.
The thermogravimetric results were presented in the form of TG, DTG, DSC and DTA curves,
respectively, where: TG - thermogravimetry presents the weight loss of studied samples in contrast
to the initial mass under increasing temperature, DTG - differential thermogravimetry is based on
the rate of weight loss, DSC - differential scanning calorimetry additionally allows for the
determination of thermal effects (endothermic and exothermic), DTA - differential thermal analysis
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is suited for the determination of characteristic temperatures. The TG, DTG, DSC, and DTA curves
were used in order to assess the thermal characteristics of the studied samples. Thermal analysis is a
very useful technique for describing the combustion processes of fuel because the results provide
rapid information about the fuel value, the temperatures at which combustion starts and ends, and
other characteristics such as maximum reactivity temperature, ash amount and total combustion
time.

3 Results

3.1.1 Product characteristics

The physical and chemical properties including proximate and ultimate analysis, and the fuel
and energy parameters of raw Miscanthus Giganteus and hydrochars obtained under various
conditions of hydrothermal carbonization are summarized in Table 1.

Table 1
Physical and chemical properties of raw Miscanthus and hydrochars.
Parameters Miscanthus HTC_4 HTC_2 HTC_3 HTC_4 HTC_6 HTC_12 HTC_4
Temperature, C 180 200 220
Residence time, h 4 2 3 4 6 12 4
Proximate analysis,
wt (%)
FC 6.77 15.52 20.18 21.29 21.74 22.03 23.82 24.34
VM 84.10 81.70 75.82 74.47 75.01 75.82 74.95 73.23
Ash 1.75 1.3 1.75 1.79 0.88 0.59 0.83 1.05
M 7.38 1.48 2.25 2.45 2.37 1.56 0.4 1.36
Fuel ratio
FC/VM 0.08 0.19 0.27 0.29 0.29 0.29 0.32 0.33
Ultimate analysis,
wt (%)
C 46.30 53.5 54.9 56 56.6 57.5 58.7 63.00
H 5.93 5.93 5.9 6.17 5.91 5.96 6.07 5.77
N 0.362 0.068 0.161 0.292 0.11 0.26 0.213 0.27
S 0.09 0 0 0 0 0 0 0
Oa 45.57 39.21 37.3 35.75 36.50 35.02 35.4 29.91
Atomic ratio
H/C 1.54 1.33 1.29 1.32 1.25 1.24 1.24 1.10
O/C 0.74 0.55 0.51 0.48 0.48 0.46 0.45 0.36
HHV, MJ/kg 17.5 21.2 21.1 21.8 21.4 21.7 23.4 23.9
LHV, MJ/kg 16.6 20.0 19.9 20.5 20.1 20.5 22.2 22.7
Energy
- 1.21 1.20 1.24 1.22 1.24 1.33 1.36
densification ratio
Energy yield, % - 97 78 78 79 77 86 79
Mass yield, % - 80 65 63 65 63 65 58
Ash yield, % - 59 65 64 33 21 31 35
FC - fixed carbon, VM - volatile matter, M - moisture, C - carbon, H - hydrogen, N- nitrogen, S -sulphur
Oa - oxygen calculated by difference, HHV - higher heating value, LHV lower heating value

Proximate analysis, including fixed carbon, volatile matter, ash, and moisture content, is the
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most common method used to determine the quality of solid fuels. The volatile matter and fixed
carbon presented in proximate analysis are two important thermochemical parameters. It should be
mentioned that volatile matter content influences directly on the combustion process resulting in the
generation of pollutants emission. Generally, Miscanthus as a kind of biomass, has a high volatile
matter content (84.10%), which may cause problems when directly combusted because it decreases
energy efficiency and generates harmful emissions [39]. The results obtained for hydrochars show a
decrease in the volatile matter and ash contents, 73.23 and 0.83%, respectively. According to the
definition, the fixed carbon is the amount of combustible material remaining in the sample after
removal of moisture, volatile matter, and ash. Therefore, the fixed carbon is discussed. Regarding
the results, the fixed carbon increases with an increase in the residence time of the process for all
studied hydrochars produced at 200 C (from an initial 6.77 to 24%). The increase in the
temperature of the process, from 180, 200 to 220 C for 4 h, caused a significant increase in fixed
carbon, 15.52 to 24.34%, which was significantly better than for 12 h of residence time conducted
under 200 C. The fixed carbon were found in agreement with the HHV results since a higher
content of fixed carbon in the fuel should be reflected in higher heating value. The moisture content
in raw Miscanthus is low, c.a. 7.38%, and the hydrochars after the drying process also have a very
low moisture content. The ash yield, defined as the ratio of percentage ash in the hydrochar to the
percentage in the raw Miscanthus multiplied by mass yield, is an important factor because of the
inorganic elemental composition in biomass which can cause fouling and slagging problems and, in
consequence, corrosion of the heating equipment and a reduction in heat transfer can occur.
Lewandowski et al. [2] claims that Miscanthus ash may characterize the low ash melting point
which could be the important problem during its combustion.
According to the results, the ash yield reduction of hydrochars is evidently observed (by 65-
31%) and it decreases with an increase in residence time and temperature of the process. It is
directly related to the removal of the inorganic elemental from hydrochar into HTC-water, the
liquid phase of the hydrothermal carbonization process.
The ultimate analysis of raw and pretreated Miscanthus provides information regarding the
percentage share of carbon, hydrogen, nitrogen, sulphur, and oxygen. The carbon content increases
to 58.7 %, compared to 46.3 % in the raw sample, with a 12 h residence time of hydrothermal
carbonization. The temperature impact for carbon content is more prominent than the time of
reaction. For 4 h of residence time, the carbon content in hydrochars produced under 200 C and
220 C, are 56.6% and 63%, respectively. The sulphur content in Miscanthus and hydrochar
samples is very low, close to 0%, and its effects are negligible. The hydrogen and nitrogen contents
show little change, but a significant decrease is observed for oxygen content. During the
hydrothermal carbonization performed at 200 C, an oxygen reduction of 22% is obtained for 12 h.
However, in the case of temperature impact the reduction is more evident, the oxygen content was
reduced by around 13% at 180 C, 20% at 200 C, and 35% at 220 C. It is well known that the
thermochemical properties of solid fuels are related to its elemental analysis and they are reflected
by the HHV value. Although both HHV and LHV were conducted by bomb calorimeter (Table 1),
they can also be determined by calculations based on elemental composition [17]. The HHV values
increase with an increase of time of the reaction, which is confirmed by a higher carbon content in
the fuel. The highest comparable HHV value is obtained for 12 h and 200 C, and for 4 h and
220 C c.a. 24 MJ/kg, corresponding with the fixed carbon of the studied fuels: the higher the fixed
carbon value, the higher the obtained HHV. The LHV behaves analogously, by always being lower
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than HHV, which is a result of subtracting the heat of vaporization of the water vapour from a
higher heating value.
Energy densification and energy yield are other indicators which evaluate the effectiveness of
the HTC process in terms of energy balance. The energy densification ratio is the ratio of HHV of
hydrochar to the HHV of raw Miscanthus, whereas the energy yield is determined by a multiplied
mass yield and energy densification ratio. According to the results summarized in Table 1 the
energy densification ratio increased from 1.2 to 1.33 by increasing the time of the reaction, and 1.22
to 1.36 by increasing the temperature by around 20 K. Applied higher temperatures of HTC process
promote the dehydration, decarboxylation, and condensation reactions of coalification process thus
resulting in energy densification. In this case it can also be seen that the percentage of energy yields
is more or less on the same level c.a. 78%. The highest energy yield, 86%, is at the higher residence
time of 12 h. A value of 79% is obtained for both studied temperatures of the process. It can be said
that during the hydrothermal carbonization process energy yields did not change significantly over
the residence time and temperature range studied.

Table 2
Properties of raw and torrefied Miscanthus.
Parameters Miscanthus TM_230 TM_260 TM_290
Temperature, oC 230 260 290
Residence time, h 0.5 1 1.5 0.5 1 1.5 0.5 1 1.5
Ultimate analysis,
wt (%)
C 46.30 50.3 50.4 51.6 51.8 52.9 55.9 55.9 57.7 62.2
H 5.93 6.08 5.73 5.86 5.9 5.89 5.62 5.81 5.07 4.83
N 0.362 0.138 0.215 0.279 0.088 0.13 0.257 0.219 0.367 0.435
S 0.09 0 0 0 0 0 0 0 0 0
O a 45.57 43.48 43.65 42.26 42.21 41.08 38.22 38.07 36.86 32.53
Atomic ratio
H/C 1.54 1.450 1.364 1.363 1.367 1.336 1.206 1.247 1.054 0.932
O/C 0.74 0.648 0.650 0.614 0.611 0.582 0.513 0.511 0.479 0.392
HHV, MJ/kg 17.5 20.03 19.96 20.53 20.61 21.09 22.31 22.42 22.75 24.57
Energy
- 1.08 1.08 1.11 1.12 1.14 1.21 1.21 1.23 1.33
densification ratio
Energy yield, % - 98 95 90 90 88 80 79 63 60
Mass yield, % - 90 88 81 81 77 66 65 51 45
O - oxygen calculated by difference
a

Table 2 presents the properties of raw and torrefied Miscanthus at temperatures of 230, 260 and
290 C and residence time of 0.5, 1 and 1.5 h. The elemental analysis is also presented. The carbon
content in all cases increased as temperature and residence time increased (Fig. 4) influencing the
HHV, which consequently increased from 17.5 to 23 MJ/kg, whereas the hydrogen content showed
a decrease (c.a. 6 to 4.83%).

Table 3
Physical and chemical properties of raw Miscanthus and pyrochars.
Parameters Miscanthus SP_350 SP_400 SP_450 SP_500
Temperature, oC 350 400 450 500
Residence time, h 0.5 1 1.5 0.5 1 1.5 0.5 1 1.5 0.5 1 1.5
Ultimate analysis,

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wt (%)
C 46.30 71.3 74.2 74.5 75.8 75.9 77.0 76.4 78.8 79 81.6 82.5 83.1
H 5.93 4.77 4.45 4.43 4.30 4.18 4.27 4.33 3.79 3.73 3.67 3.55 3.48
N 0.36 0.47 0.54 0.43 0.45 0.41 0.44 0.33 0.49 0.54 0.49 0.46 0.54
S 0.09 0 0 0 0 0 0 0 0 0 0 0 0
Oa 45.57 23.46 20.81 20.64 19.45 19.51 18.29 18.94 16.92 16.74 14.24 13.49 12.88
Atomic ratio
H/C 1.54 0.80 0.72 0.71 0.68 0.66 0.67 0.68 0.58 0.57 0.54 0.52 0.50
O/C 0.74 0.25 0.21 0.21 0.19 0.19 0.19 0.19 0.16 0.16 0.13 0.12 0.12
HHV, MJ/kg 17.5 38.22 39.63 39.80 40.44 40.31 41.18 40.89 41.52 41.55 43.15 43.51 43.77
Energy
- 2.08 2.16 2.17 2.20 2.20 2.24 2.23 2.26 2.26 2.35 2.37 2.39
densification ratio
Energy yield, % - 132 146 153 149 154 158 158 167 167 182 191 193
Mass yield, % - 63 68 71 68 70 70 71 74 74 77 81 81
Oa - oxygen calculated by difference

The preliminary study of the slow pyrolysis process was conducted at temperatures of 350,
400, 450, and 500 C, and at 0.5, 1 and 1.5 h of residence time. The properties of raw Miscanthus
and pyrochars are presented in Table 3. The increase of carbon content in pyrochars is shown in
Fig. 5, where the impact of temperature and residence time is depicted and compared to the
torrefaction case (Fig. 4). It is well seen that the temperature impact is the most impressive,
although with increasing residence time the carbon content also slightly increased. The increase in
carbon content is expressed in the increasing of HHV results. The hydrogen content in all studied
cases decreased compared to raw biomass, the lowest value 3.48% to 5.93%, respectively.
Regarding the results, the following can be assumed: the residence time of 1 h is optimal and can be
applied, and then the pretreated samples can be prepared for further investigation and discussion.

Fig. 4. Carbon content under temperature Fig. 5. Carbon content under temperature
and residence time of the torrefaction process. and residence time of the slow pyrolysis process.

The fuel character of the obtained hydrochars, torrefied Miscanthus and pyrochars versus raw
Miscanthus compared to coal can be viewed in the Van Krevelen diagram, which provides
information about the influence of elemental composition on fuel characteristics and the chemical
transformations such as demethanation, dehydratation and decarboxylation of the carbon rich
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material. Thus, the impact of hydrothermal carbonization, the torrefaction process, and slow
pyrolysis on the properties of the studied samples is evident. The diagram depicts the atomic ratios
(H/C) to (O/C) of studied samples in Fig. 6. From this diagram it can clearly be observed that all
studied processes hydrothermal carbonization, torrefaction, and slow pyrolysis improved the fuel
properties: each hydrochar, torrefied material and pyrochars obtained under studied conditions
moved from raw Miscanthus towards coal. The temperature effect can clearly be seen, the
hydrochars, torrefied Miscanthus samples and pyrochars are closer to the referenced fuel, which is
coal. The samples, which are the closest to coal are all samples produced at the highest temperature
range of the chosen processes: the hydrochar produced during 4 h at a temperature of 220 C, the
torrefied Miscanthus obtained at 1h and 290C and the pyrochar made at 1h and 500 C,
respectively.

Fig. 6. Van Krevelen`s diagram.

The solid, liquid and gaseous HTC products were characterized by their smelly, smoke-like
odour. The colour of solid products was brown, which darkened with an increased time of reaction.
A similar colour for solid products was observed for 12 h at 200 C as well as for 4 h, and 220 C.
After the drying process of the hydrochars, the odour was less evident. Apparently, some organic
compounds in HTC water, e.g. ethanol and acetic acid, have been evaporated. The size and shape of
the particles of pretreated Miscanthus were similar to the raw sample. The shape of the particles
were similar in size, but were slightly thinner depending on the reaction time.
In order to characterize the HTC-water in all studied liquid samples some parameters were
assessed. The results of pH, conductivity tested for both HTC-water and its distillate are
summarized in Table 2. According to the liquid chromatography analysis the main compound in the

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liquid is acetic acid, with the addition of other organic compounds, e.g. ethanol, furfural etc. It is
confirmed by the acid-base titration of distillates, where acetic acid is found at a concentration of
c.a. 0.085 ml/dm3. Moreover, the pH of the HTC-water in general is acidic pH 3.2-3.56. The longer
the residence time of HTC, the higher pH is found. In addition, the pH of the distillates is lower
across the whole range of studied conditions c.a. 2.85. This can be explained by the considerable
distillation of acetic acid. The conductivity of all samples was also investigated. In all of the studied
distillate samples the conductivity is 2 to 3 times lower than the parameters measured for HTC-
water. The results suggest that most inorganic compounds do not distillate. COD (Chemical Oxygen
Demand) was measured in only three samples, 4 h at 180 C, 12 h at 200 C, and 4 h at 220 C. The
resulting values are very high (19, 16.5 and 15 gO2/dm3) indicating that the HTC-water contains a
high concentration of organic matter and nutrients. COD was also measured in distillates of the
discussed samples. Its value was 2 to 3 times lower than in HTC-water. The HTC-water could
potentially be used to heat up the reactor or to produce biogas, as suggested by Oliveira [11].

Table 4
Parameters to characterize the HTC-water and its distillate.
Parameters HTC_4 HTC_2 HTC_3 HTC_4 HTC_6 HTC_12 HTC_4
Temperature, C 180 200 220
pH 3.31 3.2 3.19 3.15 3.43 3.56 3.41
pHdistillate 2.92 2.90 2.75 2.7 2.84 2.87 2.83
Conductivity, mS 3.56 2.6 4.18 2.25 2.18 2.78 2.78
Conductivitydistillate, mS 0.97 0.96 0.94 0.99 0.94 0.86 0.85

The selected samples of gaseous phase were trapped in a Tedlar bag and analyzed by GC.
According to the results, the main compound in the gaseous phase is CO2 c.a. 70%, the other
compounds are N2<30%, O2<1%, CH4<0.015%, and CxHy<1%.
Additionally, the carbon balance was studied for HTC_12 h and 8.13% of C content in the
solid phase was found, whereas just 13.75% in liquid and 4.11% in the gaseous phase.
Analysing the solid, liquid and gaseous products of studied pretreatment processes it can be
assumed that HTC, torrefaction and slow pyrolysis are generally friendly environment technologies.
Solid products consist mainly of carbon and hydrogen giving during combustion CO2 and H2O,
whereas the impact of sulphur and nitrogen is negligible. The kind and concentration of gaseous
products are not harmful. Unfortunately, the liquid products characterize the acid reaction and have
undesirable environmental impact.

3.1.2 TG/DTG/DSC/DTA study

In order to study the thermal behaviour of raw Miscanthus and hydrochars and torrefied
Miscanthus during combustion, thermal analysis was used. The results are presented in TG, DTG,
DSC and DTA curves. The detailed results for chosen hydrochars and torrefied Miscanthus during
combustion are presented in Table 5. Fig. 7 presents the combustion process for raw Miscanthus
using TGA.

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Fig. 7. The TG/DTG/DSC results for Miscanthus.

The TG of hydrochars obtained at 200 C for 2, 3, 4, 6, 12 h and at 220C for 4 h of the HTC
process are summarized in Fig. 8.

Fig. 8. The TG results for raw Miscanthus and hydrochars obtained under 2, 3, 4, 6 and 12 h at 200 C, and
4 h at 220 C of the HTC process.

It can be seen that the TG of raw Miscanthus slightly differs from other studied hydrochars, but
the shape and character is similar. The raw Miscanthus and hydrochar combustion process take
place in three main stages: at the beginning of decomposition, main decomposition and final
decomposition (Fig. 7, 8). The first stage, corresponding to the moisture content, takes place up to
c.a. 150 °C, and the mass loss does not exceed 7%. In the case of hydrochars the changes connected
with moisture loss are not significant, which is a result of the HTC process (less than 3%) thus
confirming the hydrophobic properties of pretreated biomass. The main decomposition during the
combustion process is within the 260-500 °C temperature range. The maximum weight loss
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between the observed Miscanthus is due to degradation of its basic organic components such as
hemicellulose, cellulose, and lignin. Mass loss occurs due to a release of CO2, CH4 and H2O, and
the gases formed during the decomposition of hemicellulose (190-320 °C), cellulose (280-400 °C)
and lignin (320-450 °C) [40]. The majority of hemicellulose weight loss can be observed at above
200°C for the biomass samples, which corresponds with Achaya et al. [41] who suggest that
hemicellulose produces less tars and char due to its low degradation temperature range compared to
that of the cellulose. The second stage shows the presence of two main effects. Two of the
maximum weight loss rates occur at 300 and 420 °C, which are confirmed by two exothermic
effects, 310 and 420 °C, connected with the oxidation of organic matter (Fig. 9). The mass loss after
the main stage is c.a. 80%. Above 480 °C there is no significant mass change observed for
Miscanthus. It can be assumed that above 500 °C the combustion process is finished for all studied
samples. The ash content for Miscanthus is c.a. 8%, whereas for hydrochars less than 5%. Despite
the combustion of hydrochars taking place within a narrower temperature range, the ash content is
evidently lower, which is an advantage for the combustion of the HTC product.

Fig. 9. The DSC results for raw Miscanthus and hydrochars obtained under 2, 3, 4, 6 and 12 h at 200 C,
and 4 h at 220 C of the HTC process.

The detailed results for hydrochars obtained after the HTC process are presented in Fig. 10-13,
where the TG/DTG/DSC/DTA results are shown. Based on the data in these Figs., changes in the
main stage can be observed. In Fig. 10 for 4 h at 180 °C the thermal behaviour of hydrochar is
different from the other hydrochar samples. The combustion process takes place within a higher
temperature range, and one wide exothermic peak can be observed. In Fig. 11, for 4 h at 200 °C, the
exothermic effect is higher in the first significant peak of the combustion process, whereas the
second thermal effect is much lower. On the other hand, with a longer residence time (12 h), the
thermal effects have a different outcome e.g. the first DSC peak is lower, the second is higher. This
suggests that the properties of hydrochar are more comparable to coal. When drawing a comparison
between the three temperatures, 180, 200 and 220 °C, for the same reaction time of 4 h, the effect of
carbonization is more prominent. Thus, it can be concluded that the effect of temperature is
significant.
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Fig. 10. The TG/DTG/DTA results for hydrochar obtained under 4 h at 180 C of the HTC process.

Fig. 11. The TG/DTG/DSC results for hydrochar obtained under 4 h at 200 C of the HTC process.

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Fig. 12. The TG/DTG/DSC results for hydrochar obtained under 12 h at 200 C of the HTC process.

According to Fig. 13 there are two crucial points in the main stage of combustion, where two
maximums of rate reaction are observed, for 310 and 430 °C, compared to the other analyzed
results.

Fig. 13. The TG/DTG/DSC results for hydrochar obtained under 4 h at 220C of the HTC process.

The thermal behaviour of torrefied Miscanthus is presented in Figs. 14-17. Fig 14 presents the
differences in mass changes (TG curves) of torrefied Miscanthus obtained at 230, 260 and 290 °C,
respectively (to observe the torrefaction temperature impact). The character and changes of mass
loss during combustion of torrefied samples are similar in each case. At the beginning of the
combustion, the mass loss connected with moisture release is not observed, which confirms the
hydrophobic properties of the torrefied samples.
The TG curve of torrefied sample obtained at 290 °C moves towards higher temperatures
confirming higher amount of carbon. The amount of solid residue for all the studied samples is very
low and almost nearly the same amount.

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Fig. 14. The TG results for torrefied Miscanthus obtained under 1 h at 230, 260 and 290 C of the torrefaction
process.

Fig. 15, 16 and 17 present the TG/DTG/DTA curves combustion process of torrefied
Miscanthus obtained at 230, 260 and 290 °C during 1 h of torrefaction. DTG curves enable
observation of the differences in thermal behaviour in the second stage of this process. As the
temperature and shape of the first peak is similar, the second one is evidently different. This
suggests that the decomposition of organic matter is varied.

Fig. 15. The TG/DTG/DTA results for torrefied Miscanthus obtained under 1 h at 230 C of the torrefaction
process.

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Fig. 16. The TG/DTG/DTA results for torrefied Miscanthus obtained under 1 h at 260 C of the torrefaction
process.

Fig. 17. The TG/DTG/DTA results for torrefied Miscanthus obtained under 1 h at 290 C of the torrefaction
process.

Table 5
Characteristic parameters obtained from TG and DTG profiles of studied raw Miscanthus and pretreated (HTC and
torrefaction) samples during the combustion process (air atmosphere); Tm, temperature of the maximum weight loss
rate; DTGmax, maximum weight loss rate.
Sample Tm, C -DTGmax, %/min Weight loss, % Solid residue,
%
Miscanthus 75.0 1.1 2.5 5.5
321 10.2 49.0
423 11.5 82.3
HTC_4 h
HTC_180 C 85.4 0.3 1.2 1.2
320.7 10.5 31.0

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510.0 2.5 78.2
HTC_200 C 83.6 - 4.6 3.2
315.5 42.5 32.5
481.02 4.8 84.3
HTC_220 C 80.0 - 3.5 0.4
310.9 19.5 29.4
433 17.6 73.7
Torrefied Miscanthus_1 h
TM_230 C 81.2 0.70 2.2 3.4
312.1 8.13 37.3
432.2 2.98 79.8
TM_260 C 83.6 0.6 1.8 3.6
309.3 8.7 33.6
418.7 2.9 70.0
TM_290 C 80.0 0.4 2.5 4.5
305.5 5.4 21.6
419.1 3.7 62.0

4 Conclusion

The results show that hydrothermal carbonization and torrefaction are the most promising
methods for upgrading biomass, in this case Miscanthus, through its conversion into an energy-
dense solid fuel. The physical and chemical properties of the hydrochars and torrefied Miscanthus
produced under different conditions were found to be comparable to a more coal-like fuel, and
exhibited favourable combustion behaviour confirmed by thermal analysis TG/DTG/DSC/DTA.
The results confirmed that the temperature impact is greater than the residence time of the HTC
process. In the case of torrefaction and based on the preliminary study of slow pyrolysis the
temperature impact was also prominent. Therefore, the carbonization of biomass improves not only
the energy content of biomass, but also its properties for easier handling, transportation and storage.
Additionally, carbonized biomass is easily grindable, leading to a more friendly feedstock for
thermal processes. This work suggests that the HTC, torrefaction and presumably slow pyrolysis
processes have potential for the conversion of biomass for use in a variety of applications including
energy generation by combustion or gasification.
One of the key outcomes of this work is better understanding of pretreatment processes of
energy crop, giving detailed analysis of carbonaceous products. It is worth mentioning that a novel
approach of this study is a comparison of HTC, torrefaction and slow pyrolysis of Miscanthus
Giganteus taking into account combustion properties of obtained products. The presented
investigations and results could be helpful during selection of pretreatment process for renewable
fuels.

Acknowledgements

The work was supported by grant AGH no. 11.11.110.423.

The Authors are grateful to EKOPROD Ltd. the proprietor of the HTC apparatus used in the
presented study. The Authors also wish to thank Dr. Marcin Gajek for TGAs analysis.

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