Fuel 252 (2019) 635–645

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Fuel
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Full Length Article

Laboratory studies on the influence of biomass particle size on pyrolysis and T

combustion using TG GC/MS
⁎
Agata Mlonka-Mędrala , Aneta Magdziarz, Tadeusz Dziok, Małgorzata Sieradzka,
Wojciech Nowak
AGH University of Science and Technology, Mickiewicza 30 Av., 30-059 Krakow, Poland

A R T I C LE I N FO A B S T R A C T

Keywords: The agriculture residues and energy crops have significant energy potential, which is not enough used so far. The
Agriculture biomass agriculture production in Poland, and other countries of EU, gives a huge amount and variety of agriculture
Energy crops wastes. Whereas, energy crops characterise large annual growth at low-quality soil and high energy yields per
Particle size unit of area. For this study three different agriculture biomass and two energy crops were selected. The samples
Pyrolysis
were characterized in terms of their proximate and ultimate analysis. The main aim of this paper was to in-
Combustion
TGA-GC/MS
vestigate the influence of biomass particle size distribution on the combustion and pyrolysis processes using
thermogravimetric analysis (up to 600 °C at 5, 10 and 20 K/min or 50 K/min heating rate). Two fractions of
biomass samples were investigated, smaller (S) size of major fraction smaller than 0.09 mm and sample of
particle size smaller than 0.425 mm named larger (L). The gaseous products generated during pyrolysis process
were analysed with GC/MS. Additionally, the kinetics analysis of studied processes was performed. Finally, it
was found the particle size influences on the TG/DSC results and consequently significantly on the activation
energy of combustion and slightly on pyrolysis of studied biomass samples.

1. Introduction cultivation of perennial grasses on reducing leaching of heavy metals to

Biomass is an organic material, which can be divided into the fol-
lowing groups: wood and wood wastes; the organic part of municipal
solid waste; the organic part of industrial waste; sewage sludge;
manure; energy crop plants and plant by-products of food production.
In a longer perspectives the demand for biomass energy will be in-
creased because of environmental protection and EU law regulations.
According to Polish Energy Policy Until 2030 (EPP 2030), the National
Renewable Energy Action Plan 2010, and Renewable Energy Sources
Act 2015, Poland is focused on the biomass as a renewable energy
source and the wood-derived biomass has the biggest energy potential.
Nevertheless agriculture biomass has lower energy intensity than wood
it can bring the energy benefits, too [1,2]. Agriculture biomass and
energy crops have been starting to play an essential role in bioenergy
production. In Poland, the cereal crops dominate in agriculture pro-
duction, therefore the straw potential is very wide and it concludes the
following plans: wheat, barley, triticale, rye, oats, mixed cereals, maize,
rapeseed and turnip rape [3]. In addition to agriculture biomass the
energy crop plants are potential energy source with extra role in phy-
toremediation of contaminated soil. Energy crops can help in
groundwater and have ecological capabilities affecting the physical and
chemical properties of the soil [4].
Thermal conversion (combustion, pyrolysis and gasification) are the
most common biomass utilization technologies in the industry. In
Poland, biomass combustion is commonly used for buildings heating
systems and water heating by individual customers [5]. Gasification
and pyrolysis are alternative technologies for energy production from
solid biomass. Pyrolysis is a process of a thermochemical decomposition
of biomass into other, useful products, the process is carried out in the
complete absence of an oxidizing agent [6]. Pyrolysis of the biomass
allows to obtain three main products: solid (bio-char), liquid (bio-oil)
and gaseous (syngas) [7,8]. Produced syngas can be used for many
purposes, i.e. power generation, production of liquid and gaseous fuels
or can be widely used in the chemical industry [9–11]. The gasification
process is carried out at the temperature above 800 °C with the use of a
gasifying agent, mainly steam, but also air, oxygen, carbon dioxide or
mixtures, which has influence on the composition of syngas and its
quality [12,13]. In comparison to gasification, pyrolysis occurs at re-
latively low temperature range (300–600 °C). High temperature and
long residence time promote gas production as the main pyrolysis

⁎
Corresponding author at: AGH University of Science and Technology, Mickiewicza 30 Av., 30-059 Krakow, Poland. Tel.: +48 12 617 41 75.
E-mail address: amlonka@agh.edu.pl (A. Mlonka-Mędrala).

https://doi.org/10.1016/j.fuel.2019.04.091
Received 31 January 2019; Received in revised form 31 March 2019; Accepted 16 April 2019
Available online 07 May 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
A. Mlonka-Mędrala, et al. Fuel 252 (2019) 635–645

product, while low temperature and long residence time promote the Table 1
formation of char. Formation of tars proceeds in larger scale in medium Proximate analysis of selected biomass samples, wt. %.
temperature range, short residence time and with high heating rate Sample Ma(L) Ma(S) Aa VMa VMdaf
[14]. During pyrolysis process, large and complex hydrocarbon mole-
cules break down into smaller and more simple molecules of gas, liquid, MCS1 7.4 6.6 10.6 67.3 82.1
MCS2 9.0 6.0 10.0 64.8 80.0
and char [14]. Main advantages of gasification and pyrolysis over a
CS 10.3 7.6 13.3 65.5 85.7
traditional combustion are pathogens destruction, size and volume re- MxG 7.2 6.6 5.0 71.1 81.0
duction and lower environmental impact [15]. SV 7.1 6.1 1.4 74.0 80.9
It should be pointed out, that process parameters as well as fuel
properties have significant influence on the combustion, pyrolysis and
gasification processes main products yield. Biomass particle size affect Table 2
mainly the process kinetics [16,17]. Fuel analysis of selected biomass samples, wt. %.
Biomass size reduction is one of the most frequently used technique Sample Nad Cad Had Oad Clad Sad
of mechanical pre-treatment, during the process the material bulk
density together with energy density are increased and the transport MCS1 0.89 49.32 6.64 42.70 0.324 0.134
MCS2 0.95 47.46 6.89 44.21 0.420 0.136
costs might be reduced [18]. Biomass densification into pellets or bri-
CS 0.67 46.86 6.54 45.54 0.308 0.080
quettes is an effective way to minimize problems with dusting during MxG 0.67 51.86 7.02 40.29 0.091 0.084
transportation and storage. By means of pre-treatment and pre-pro- SV 0.31 49.39 6.78 43.46 0.019 0.040
cessing methods cellulose, hemicellulose and lignin matrix in lig-
nocellulosic biomass can be modified. On the market there are many
types of mills: ball mills, hammer mills, knife mills, ring-roller mills and and kinetics analysis was done. Additionally, for pyrolysis process, the
other used for biomass size reduction. The most important factor de- application of TG GC/MS allowed to correlate the materials thermal
termining suitable technology for biomass size reduction is the initial behaviour with pyrolytic gas composition. The focus was on the char-
moisture content in the material [18,19] and initial particle size [20]. acterization and comparison of different kind of biomass.
Biomass grinding is still a challenging procedure in the industry, many
additional pre-treatment techniques are applied to increase the initial 2. Materials and methods
raw biomass grindability [21].
Additionally, according to Yuan et al. (2016) milling is the method 2.1. Materials
of mechanical biomass activation [22]. It affects biomass properties:
total surface area and pore size [23] as well as crystalline structure of Five kinds of biomass ashes were considered for this study: three
biomass [22,24]. Additionally, grinding process changes the biomass agricultural biomass and two energy crops. The samples were denoted
properties by increasing the accessibility to cellulose [19]. Milling also as MCS1 – mixed cereal straw 1, MCS2 – mixed cereal straw 2, CS – corn
enhances chemical reactivity of biomass [22]. Therefore, the particle straw and MxG – Miscanthus × giganteus and SV – Salix viminalis.
size of biomass affects the kinetics of combustion, gasification and
pyrolysis processes. 2.2. Methods
The particle size of biomass plays a significant role in particle flow
and flame propagation in the combustion and gasification processes Proximate analysis of biomass samples was determined according to
[16]. Reducing the particle size of biomass increases incineration Polish standards: PN-EN ISO 18134-3:2015-11, PN-EN ISO 18123:2016-
temperature and velocity [25]. For larger particles, there is an increase 01 and PN-EN ISO 18122:2016-01. The moisture content of the selected
in thermal resistance that extends the particle heating time [25], what fuels was determined for the samples after first stage of the milling
may be a reason of an incomplete conversion [26]. Moreover, the process in the knife grinder with a 0.425 mm sieve denoted with a su-
particle size of biomass also affects the release of trace elements [27]. perscript L – large and for the samples after the second stage of the
The impact of woody biomass particle size on the pyrolysis process milling process in a ring-roller mill denoted as S – small.
was studied in detail by [17,28,29]. It was shown that material particle The carbon, hydrogen, nitrogen and sulphur content were de-
size has a significant influence on the activation energy, gas composi- termined using Truspec CHN628 Leco analyser. Chlorine content in fuel
tion and the product yield distribution. Volatiles yields decrease with was determined according to PN-EN 15289:2011. The results of prox-
increasing particle size [29], what may be explained by mass transfer imate and ultimate analysis are shown in Tables 1 and 2, respectively.
limitations of the volatiles evolving during pyrolysis. The particle size The first part of this study was to determine lignocellulosic mate-
of biomass also affects bio-oil production in pyrolysis: yield of bio-oil rials size reduction procedure to obtain very fine material < 0.1 mm.
and its quality [30]. It also play a significant role in bed agglomeration The motivation was that in some cases very fine size of the sample is
in fluidized bed reactor [31]. On the other hand, according to Septien required and the interference into the fuel structure will definitely af-
et al., the particle size of biomass (0.35–0.80 mm) does not influence on fect also the kinetics of thermal conversion technologies like combus-
gas composition in fast pyrolysis at high temperature [26]. tion or pyrolysis. For this study several laboratory scale mills listed in
It has to be mentioned, that not only particle size affects biomass Fig. 1 were tested.
behaviour during thermal conversion processes but also the particle size Biomass, especially straw is a very hard and fibrous material.
distribution [20,32] and shape as well [29]. Due to the larger internal Manual grain grinder and impact mill are both suitable for small por-
temperature gradients in a single grain, shape becomes more important tions of fuel, but the particle size of obtained fractions was not sa-
for larger particle sizes [33]. tisfactory. Any changes in sample size and grinding time did not give a
Taking into account the presented issues concerning biomass the sufficient improvement in the size reduction. Application of smaller
knowledge of biomass fuel particle size influence on thermal conversion sieve size (smaller than 0.425 mm) in a knife grinder caused material
processes is necessary to control and predict the pathways, kinetics and retention in the apparatus, the capacity was very poor and a re-
gas composition during these processes. In order to provide a broaden presentative sample was hard to obtain. Grinding in a ball mill did not
description of this issue, a new approach was presented. In this study give good results. Increasing the grinding time caused the apparatus
the influence of herbaceous biomass of agricultural origin and energy heat up and no improvement of size reduction was observed.
crops particle size on the thermal conversion processes (combustion Additionally, an increase of grinding time may cause attrition of steel
and pyrolysis) using simultaneous thermal analysis was investigated apparatus components and the contamination of sample might be

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A. Mlonka-Mędrala, et al. Fuel 252 (2019) 635–645

Fig. 1. Biomass milling procedure.

Table 3
Conditions of performed STA experiments.
Sample Process Atmosphere Sample mass, mg Heating rate, °C/min Residence time, min Temperature range, °C

MCS1, MCS2, CS, MxG, SV combustion Oxidizing: Synthetic air, 50 ml/min ∼5 5, 10, 20 – 25–800
MCS1, MCS2, CS, MxG, SV pyrolysis Inert: Nitrogen, 50 ml/min ∼5 10, 50 30 25–600

Fig. 2. Particle size distribution after first (L) stage milling procedure, wt. %.

observed. Cryogenic mill was used to check if freezing of sample with
liquid nitrogen will increase its brittleness. The analysed samples were
characterized by a moderate moisture content and the use of cryogenic
mill did not enhanced the grindability of the fuel.
The most suitable apparatus for size reduction of the selected bio-
mass samples was a laboratory ring-roller mill (EKO – LAB TEST-LAB-
09) used for grinding medium and very hard materials. The grinding
process is performed in the apparatus closed working vessel with 3
stainless steel rollers (grinding elements). The working vessel filled
with the material is attached to the upper part of the vibrating appa-
ratus. Grinding time depends on the type of the material, sample size,
its initial particle size distribution and the required final particle size.
The grinding time of the pre-ground samples analysed in this work, was
set to 6 min. Samples after final stage milling procedure in a ring-roller
mill were denoted as (S) and samples after the first milling stage in a
knife grinder with a 0.425 mm sieve were denoted as (L). In order to
determine the biomass samples particle size distribution, a vibrating
sieve machine MULTISERW-Morek LPzE-2e was used, measurements
were taken in 2 sets of 4 min., each. It is worth to mention that biomass
is less brittle than fossil fuels and obtained fraction is not spherical in
shape. Therefore, some particles of larger size (cylindrical shape)
passed through the sieves increasing the incorrectness of the obtained
results.
The Simultaneous Thermal Analysis (STA) was performed to ob-
serve the kinetics of biomass thermal conversion technologies: com-
bustion and pyrolysis. The STA technique combines the thermogravi-
metric analysis (TGA) – continuous mass measurement with differential
scanning calorimetry (DSC) – continuous heat flow measurement, both

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A. Mlonka-Mędrala, et al. Fuel 252 (2019) 635–645

Fig. 3. Particle size distribution after second (S) stage milling procedure, wt. %.

Fig. 4. STA results of MCS1 sample combustion process.

in function of temperature and in a controlled atmosphere. In the
presented study, the thermogravimetric analysis was combined with gas
chromatography and mass spectrometry. Such combination of analy-
tical methods allows to correlate thermal effects with information about
released gas composition. TGA and DSC are frequently used techniques
to determine thermal decomposition of fuels in oxidizing (combustion,
gasification) and inert (torrefaction, pyrolysis) atmospheres [34–38].
During the STA analysis a series of gas samples were collected, stored
and analysed by GC/MS. For a comparative study purposes, sampling
temperature range: 200–350 °C was set the same for all samples.
All samples were tested in oxidizing (combustion conditions) and
inert (pyrolysis conditions) atmosphere to determine the influence of
biomass sample particle size distribution on the kinetics of these pro-
cesses. All experiments were carried out at atmospheric pressure, more
details concerning the STA process conditions are presented in Table 3.
Based on thermogravimetric data the kinetic parameters such as
activation energy (Ea) and pre-exponential or frequency factor (k0)
were obtained by methods for analysing non-isothermal solid-state ki-
netic. Solid state kinetic data are the major interest in thermal pro-
cesses. The kinetics of biomass has been studied by many research
groups [39–41].
The kinetic description of a reaction was based on the following
assumptions. The reaction rate is defined as the change in conversion
per unit time, and it is a function of the conversion α:
dα
= k (T ) f (α )
dt (1)
The temperature dependence of the reaction rate constant, k, is
described by the Arrhenius equation:
Ea
k(T) = k 0e− RT (2)
where k is the chemical reaction rate constant, Ea is the apparent

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Fig. 5. STA results of MCS2 sample combustion process.

Fig. 6. STA results of CS sample combustion process.

activation energy (kJ mol−1), T is the absolute temperature (K), k0 is is calculated by an iteration process, and the pre-exponential factor is
the pre-exponential factor (s−1) and R is the universal gas constant. calculated as follows:
Assuming β as the heating rate: EA
e− RT
dT k 0 = β ·EA·
β= RT 2 (5)
dt (3)
The order of reaction is assumed to be 1.
and substituting k by the Arrhenius equation in the rate equation gives
the fundamental expression (4) of analytical methods to calculate ki- 3. Results
netic parameters, on the basis of the TG results:
dα A Ea The studied biomass samples were typical Polish agriculture mate-
= ·f (α )·e− RT rials and energy crops. All samples were characterized by similar
dT β (4)
proximate and ultimate parameters with slight differences only (Tables
The studied processes were described with the ASTM E698 method 1 and 2). Agriculture biomass samples were characterized by a sig-
(Standard Test Method for Arrhenius Kinetic Constants for Thermally nificant amount of ash (more than 10%) and lower volatile matter
Unstable Materials). The method enables to determine the kinetic data content, whereas energy crops had very low ash content and higher VM.
from the DTG peak temperature from a TGA step. The activation energy The ash content and its chemical composition are significant issues

639
A. Mlonka-Mędrala, et al.
Fig. 7. STA results of MxG sample combustion process.
Fig. 8. STA results of SV sample combustion process.
during thermal processing taking into account slagging and fouling as
well as corrosion of boiler metallic surfaces [42]. It should be noticed
that agriculture biomass had a noticeable amount of ash and chlorine
what can suggest that these kind of operational problems can appear.
Nevertheless, all studied biomass samples were characterized by high
amount of combustible elements (C and H), about 50% carbon content
and 7% hydrogen in all samples. The nitrogen content was low, less
than 1%, even 0.3% for Salix viminalis. Sulphur contents of studied
biomass were not significant. Analysing the ultimate and proximate
parameters of presented biomass it can be concluded that agriculture
biomass and energy crops can be successfully thermally converted for
energy production, however the possibility of operational problems can
occur.
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Fuel 252 (2019) 635–645
3.1. Particle size distribution
The results of the biomass samples particle size distribution de-
termined using a vibrating sieve machine were determined for all
samples and the results were shown in Figs. 2 and 3. After final grinding
procedure in the ring-roller mill more than 60% of biomass sample
were smaller than 0.09 mm. However, the worst results were obtained
for MCS2 sample, which was characterized by the highest moisture
content. It might be concluded, that higher amounts of water in fuel
influences the grinding efficiency.
3.2. Thermal analysis of combustion and pyrolysis process
Lignocellulosic materials are mainly composed of three different
fractions: cellulose, hemicellulose and lignin [43]. The content of these
organic compounds depends on the biomass origin, stage and
A. Mlonka-Mędrala, et al. Fuel 252 (2019) 635–645

Table 4 Table 6
First stage of decomposition (hemicellulose) during combustion. Third stage of decomposition (lignin) during combustion.
5 K/min 10 K/min 20 K/min 5 K/min 10 K/min 20 K/min

MCS1 (S) MCS1 (L) MCS1 (S) MCS1 (L) MCS1 (S) MCS1 (L) MCS1 (S) MCS1 (L) MCS1 (S) MCS1 (L) MCS1 (S) MCS1 (L)
tin, °C 150 150 150 150 150 150 tin, °C 412 415 432 412 418 372
tfin, °C 354 354 358 356 362 372 tfin, °C 550 550 550 550 550 550
tmax, °C 283 282 291 289 297 301 tmax, °C 434 435 456 434 456 442
Δm, % 65.49 63.73 61.93 58.76 60.30 57.86 Δm, % 5.51 8.37 6.89 11.59 9.44 25.62

MCS2 (S) MCS2 (L) MCS2 (S) MCS2 (L) MCS2 (S) MCS2 (L) MCS2 (S) MCS2 (L) MCS2 (S) MCS2 (L) MCS2 (S) MCS2 (L)
tin, °C 150 150 150 150 150 150 tin, °C 418 418 430 430 374 382
tfin, °C 360 359 368 370 374 382 tfin, °C 550 550 550 550 550 550
tmax, °C 287 286 298 297 307 309 tmax, °C 387 477 449 449 414 447
Δm, % 65.39 62.33 64.22 62.19 62.33 60.47 Δm, % 5.94 8.93 6.42 6.42 21.88 25.41
CS (S) CS (L) CS (S) CS (L) CS (S) CS (L)
CS (S) CS (L) CS (S) CS (L) CS (S) CS (L)
tin, °C 415 417 417 416 412 371
tin, °C 150 150 150 150 150 150
tfin, °C 550 550 550 550 550 550
tfin, °C 344 346 348 357 346 371
tmax, °C 431 434 439 436 447 421
tmax, °C 284 284 284 293 298 304
Δm, % 4.31 6.71 5.63 8.84 6.75 25.14
Δm, % 64.29 62.02 59.88 60.55 59.84 62.71
MxG (S) MxG (L) MxG (S) MxG (L) MxG (S) MxG (L)
MxG (S) MxG (L) MxG (S) MxG (L) MxG (S) MxG (L)
tin, °C 359 361 360 369 383 385
tin, °C 150 150 150 150 150 150
tfin, °C 550 550 550 550 550 550
tfin, °C 359 361 360 369 383 385
tmax, °C 407 412 397 415 429 437
tmax, °C 310 310 309 311 319 316
Δm, % 24.65 24.33 25.33 26.12 25.22 26.58
Δm, % 69.19 64.81 65.02 63.63 67.17 64.19
SV (S) SV (L) SV (S) SV (L) SV (S) SV (L)
SV (S) SV (L) SV (S) SV (L) SV (S) SV (L)
tin, °C 362 376 364 376 383 403
tin, °C 150 150 150 150 150 150
tfin, °C 550 550 550 550 550 550
tfin, °C 362 376 364 376 383 403
tmax, °C 416 436 414 432 429 463
tmax, °C 312 312 308 316 323 325
Δm, % 23.24 22.24 27.70 25.35 24.86 23.60
Δm, % 68.59 69.87 66.05 67.41 67.79 69.44

tin is the initial temperature of decomposition.

tfin is the temperature at which ends the decomposition.
Table 5 tmax is the temperature at which the highest decomposition rate was noted.
Second stage of decomposition (cellulose) during combustion. Δm is the mass loss percentage in a given temperature range (tin–tfin).
5 K/min 10 K/min 20 K/min
Table 7
MCS1 (S) MCS1 (L) MCS1 (S) MCS1 (L) MCS1 (S) MCS1 (L) Thermal decomposition during pyrolysis process.
tin, °C 354 354 357 357 362 –
tfin, °C 412 415 432 412 418 – 10 K/min 20 K/min 50 K/min
tmax, °C 383 385 395 385 390 – tmax, °C Δm, %
Δm, % 13.07 14.46 15.22 13.53 14.20 –
MCS1 (S) 321 327 337 65
MCS2 (S) MCS2 (L) MCS2 (S) MCS2 (L) MCS2 (S) MCS2 (L)
MCS1 (L) 323 329 338 65
tin, °C 360 359 368 370 – –
MCS2 (S) 325 331 341 65
tfin, °C 418 419 430 425 – –
MCS2 (L) 327 331 341 65
tmax, °C 387 393 398 401 – –
CS (S) 323 329 340 67
Δm, % 12.26 13.83 12.99 12.34 – –
CS (L) 325 331 341 68
CS (S) CS (L) CS (S) CS (L) CS (S) CS (L) MxG (S) 340 345 339 73
tin, °C 344 346 348 347 346 – MxG (L) 343 347 353 72
tfin, °C 415 416 417 416 412 – SV (S) 350 354 353 74
tmax, °C 383 387 384 391 381 – SV (L) 324 359 358 75
Δm, % 17.38 17.06 20.22 15.20 19.49 –

second and third stage of decomposition were determined in Tables 4–6

conditions of growth (hemicellulose: 20–40 wt%, cellulose 35–55 wt%
and lignin 10–25 wt%) [44]. Thermal decomposition of hemicellulose
might be observed within the temperature range of 150–350 °C, cellu-
lose decompose in 275–350 °C. Lignin decomposes in the highest tem-
perature range: 250–500 °C [45]. The kinetic experiments of cellulose,
hemicellulose and lignin revealed the importance of interactions be-
tween fractions. However, during STA analysis of lignocellulosic ma-
terial two or three inflection points are usually noted and the pics can
be assigned to cellulose, lignin and hemicellulose thermal decomposi-
tion [43]. In this study, despite of the interactions between the frac-
tions, during combustion process it was possible in most cases to
identify cellulose, hemicellulose and lignin decomposition.
In all cases mass reduction in the temperature range 50–150 °C was
connected with an initial moisture release. During the combustion
process of raw agricultural biomass samples (MCS1, MCS2 and CS)
three inflection points on TG curve and corresponding picks on DSC
curve were observed. The first, determines thermal decomposition of
hemicellulose, the second – cellulose and the third one corresponding
with lignin decomposition (Figs. 4–8). The mass losses during first,
respectively.
In case of energy crops, only two inflection points on TG and DSC
curves were observed, the thermal decomposition of hemicellulose and
cellulose were observed together as one joined pick on DTG curve.
TG and DTG curves for all samples show that (S) samples char-
acterised by higher content of small fractions are slightly more reactive.
However, the influence of fuel particle size on decomposition process of
hemicellulose, cellulose and lignin was very limited and no tendency
was observed. In case of combustion, the diffusion process has a high
impact on the combustion kinetics. As the sample was placed in a
crucible, the oxidizing agent (air) diffusion was limited, especially in
case of (S) samples characterized by a higher bulk density. Additional
effect was observed in case of energy crops, thermal effects of lignin
decomposition on DSC curve were shifted for (S) samples by 20–50 °C
towards lower temperatures. Fuel grinding had the greatest impact on
the thermal effects associated with the combustion process. In the case
of agriculture biomass samples, an increase in thermal effects during
the release and combustion of volatile matter was observed, whereas

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A. Mlonka-Mędrala, et al.
Fig. 9. TG and DTG results of CS and MCS1 sample pyrolysis process.
Fig. 10. TG and DTG results of MCS2 sample pyrolysis process.
during combustion of energy crops an increased thermal effect was
observed in the temperature range related to the char burnout.
During the pyrolysis process of raw biomass one inflection point on
TG curve was observed. The measured mass loss during pyrolysis pro-
cess is shown in Table 7. The obtained results are consistent with vo-
latile matter content in the analysed samples and no impact of particle
size on the mass loss was observed. For all analysed samples, a higher
heating rate caused shift of curves to higher temperatures. It is believed
that this is due the thermal hysteresis effect which is directly related to
the thermal resistance of the material [46]. A similar influence of
particle size on the pyrolysis process of straw and energy crops samples
were noticed (Figs. 9–13). For a higher particle size (L) the curves were
slightly shifted towards higher temperatures what should be explained
by an increase in heating time for larger particles size [25]. In addition,
for larger grains a mass transfer limitations of the volatiles evolving
during pyrolysis occur which can even cause a reduction in the yield of
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Fuel 252 (2019) 635–645
pyrolysis gas [29].
3.3. Kinetics analysis
Determination of the kinetic parameters (activation energy and the
Arrhenius constant) of the collected material enables to assess the
mechanical pre-treatment process influence on fuel thermal processing
kinetics. The parameters were calculated based on performed STA
analysis in oxidizing and inert atmospheres. The average activation
energy values and pre-exponential factor for combustion and pyrolysis
processes are summarized in Tables 8 and 9, respectively. The kinetic
parameters were obtained using ASTM E698 method for 3 heating rates,
for combustion: 5 K/min, 10 K/min and 20 K/min, and for pyrolysis:
10 K/min, 20 K/min and 50 K/min.
The activation energy values of the (S) and (L) samples for agri-
cultural biomass were in the range of 149.5–192 kJ/mol. The lowest
A. Mlonka-Mędrala, et al.
Fig. 11. TG and DTG results of CS sample pyrolysis process.
Fig. 12. TG and DTG results of MxG sample pyrolysis process.
values of the calculated activation energy were noted for SV sample:
99.7–139.9 kJ/mol. In most cases, except one - MCS1, the activation
energy was lower for samples (S) characterised by a smaller particle
size. It means that, as predicted, mechanical pre-treatment affect fuel
thermal behaviour and enhance fuel reactivity.
The effect of particle size on pyrolysis process was not observed, the
activation energies were very similar for both fuel fractions. The acti-
vation energies in all cases were quite similar, the lowest values were
noted for CS (S) sample = 162.8 kJ/mol and the highest for MCS1 (L) –
187.1 kJ/mol.
3.4. Released pyrolytic gases analysis (the GC/MS analysis)
The released pyrolytic gas was captured in a system of 16 heated
storage loops. A series of gas samples was taken from 200 °C up to
350 °C with the heating rate 10 K/min. The qualitative analysis of
captured gas samples was performed afterwards. The analysis shown
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Fuel 252 (2019) 635–645
that major pyrolytic gas components are: linear and cyclic ketones,
phenols, acids, furans, alcohols and other. The diversity of identified
compounds was very high, but a slight difference was noted at the
beginning of the process. The heavier (long carbon chain) compounds
were identified at the beginning of the process in case of samples: CS(S)
and MxG (S). There are two possibilities to explain this observation.
First, the heavier compounds were released earlier in case of (S) sam-
ples and second, the size reduction influences the released gas com-
position and no long carbon chain compounds were released.
The occurrence of higher hydrocarbons in the pyrolysis gas up to
270 °C was also reported at work [7]. It was also noted that for the
particle size below 1 mm (as in the presented work), the reduction of
the grain size caused an increase in the yield of bio-oil, as well as an
increase in its viscosity [30]. That increase in viscosity was related to
the occurrence of the high molar mass oligomers.
A. Mlonka-Mędrala, et al. Fuel 252 (2019) 635–645

Fig. 13. TG and DTG results of SV sample pyrolysis process.

Table 8 rates. The calculated Ea for studied biomass also demonstrated the
Kinetic parameters (Ea, k0) of biomass samples calculated for combustion pro- impact of particle size of biomass and smaller Ea was calculated for
cess. small particle size samples during combustion. Additionally, using TG
Sample k0 Ea, kJ/mol n GC/MS the gaseous products released during pyrolysis processes were
detected. A large variety of chemical organic compounds were identi-
MCS1 (S) 6.00E+15 192.24 1.00 fied in 250–350 °C range of temperature. The TG GC/MS results con-
MCS1 (L) 7.22E+13 171.55 1.00
firmed that chemical composition of gases changes during the pyrolysis
MCS2 (S) 3.64E+11 149.49 1.00
MCS2 (L) 1.88E+14 177.71 1.00 of corn straw products with the increase of temperature and moreover
CS (S) 4.13E+08 114.93 1.00 changes depending on particle size of biomass. Concluding, TG GC/MS
CS (L) 3.65E+10 137.08 1.00 allowed in an effective way to analyse the thermal conversion kinetics
MxG (S) 8.97E+10 146.60 1.00 of biomass. TG GC/MS analysis provides detailed information which is
MxG (L) 1.76E+17 216.27 1.00
SV (S) 3.54E+06 99.66 1.00
complimentary to other techniques used to analyse thermal behaviour
SV (L) 1.78E+10 139.93 1.00 of biomass and can be used in thermal decomposition studies of bio-
mass in larger scale. Furthermore, obtained results confirmed that
particle size of biomass is very important parameter and should be
Table 9 taken into account during the planning of thermal conversion processes
Kinetic parameters (Ea, k0) of biomass samples calculated for pyrolysis process. of fuels.
Sample ln(k0) Ea, kJ/mol n
Acknowledgements
MCS1 (S) 1.20E+13 172.67 1.00
MCS1 (L) 2.08E+14 187.07 1.00
This work was supported by National Science Centre, Poland (grant
MCS2 (S) 7.76E+12 171.01 1.00
MCS2 (L) 4.39E+12 168.85 1.00 no. 2016/21/N/ST8/03720) and Polish Ministry of Science and Higher
CS (S) 1.48E+12 162.76 1.00 Education [grant AGH no 16.16.110.663].
CS (L) 1.20E+13 173.50 1.00
MxG (S) 1.06E+13 177.02 1.00 References
MxG (L) 8.00E+12 175.64 1.00
SV (S) 1.80E+13 182.90 1.00
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