Bioresource Technology 278 (2019) 1–8

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Effect of torrefaction on rice straw physicochemical characteristics and T

particulate matter emission behavior during combustion
⁎
Xingping Kaia,b, Yuxia Menga, Tianhua Yanga, , Bingshuo Lia, Wanli Xinga
a
Key Laboratory of Clean Energy of Liaoning, College of Energy and Environment, Shenyang Aerospace University, Shenyang 110136, PR China
b
Key Laboratory of Ocean Energy Utilization and Energy Conservation of Ministry of Education, School of Energy and Power Engineering, Dalian University of Technology,
Dalian 116024, China

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

Keywords: In this work, the effects of different torrefaction temperatures and durations on the physicochemical properties
Biomass of rice straw (RS), and the emission characteristic of PM10 (particulate matter with aerodynamic diameters of
Torrefaction ≤10 µm) during torrefied RS combustion, were investigated. Results indicate that the release of Cl and K, and
Combustion decomposition of the organic matrix demonstrated a promoting effect during torrefaction. However, the removal
Particulate matter
of Cl and K did not reduce the emission of PM1. The emission concentration of PM1 and PM1–10 generated from
torrefied RS was enhanced, and the yields of PM1–10 was much higher than those of PM1. The concentrations of K
and Cl in PM1–10 increased with torrefaction temperature, combined with the microstructure, indicating that the
torrefaction pretreatment promoted the heterogeneous condensation of KCl vapour to form PM1–10.

1. Introduction alter the properties of biomass.

As the only renewable carbonaceous resource, biomass is widely
found on Earth and its quantity is continuing to increase. The annual
production of global biomass constitutes approximately 100 billion tons
(Sheldon, 2014), of which approximately 600 million tons are rice
straw (RS) (Yang et al., 2018). However, RS was typically discarded
randomly or treated by burning directly in open fields in the past few
years, which was not only inefficient, but also produced a large number
of fine particles causing severe haze.
In recent years, in order to enhance the recycling energy of factories
and reduce the consumption of fossil resources, biomass has been stu-
died in many research fields such as pyrolysis (Xia et al., 2018), gasi-
fication (Kai et al., 2017), high pressure liquefaction (Yang et al., 2018)
and combustion (Gao et al., 2016). Biomass combustion is the most
direct and efficient method to utilize, and is beneficial for reducing
carbon dioxide emissions. However, biomass is characterised by a high
moisture content, low heating value and strong hydrophilicity, thus
posing a significant challenge to its transportation, storage and com-
bustion. In addition, in the combustion process of biomass, chlorine and
alkali metals in biomass are easily volatilised into the gas phase and
adhere to the heat transfer surface, causing serious problems such as
deposition, scaling, ash fusion, corrosion and fine particulate matter
emission (Gao et al., 2016), thus, limiting the scale of biomass appli-
cations. Therefore, appropriate pretreatment techniques are required to
Torrefaction is a mild thermochemical treatment process to improve
the properties of solid biofuels in an inert condition under atmospheric
pressure at the temperature range of 200–300 °C (Sukiran et al., 2017;
Xu et al., 2018). Currently, torrefaction has been studied widely, fo-
cusing on the effect of torrefaction on physical and chemical properties
such as removing the moisture (Uemura et al., 2015; Valix et al., 2017),
reducing the hydrophobicity (Mei et al., 2015; Chen et al., 2018), im-
proving the carbon content and Higher Heating Value (HHV) (Song
et al., 2018; Zhang et al., 2018b; Chen et al., 2017), enhancing grinding
performance (Correia et al., 2018), and damaging fiber structure (Wang
et al., 2016; Dai et al., 2018), which is beneficial to reduce the costs of
storage and transportation and broken energy consumption, and also
improve its subsequent combustion efficiency (Mi et al., 2016). More-
over, Wang et al. (2017a,b) found that torrefaction can change the
pyrolysis product distribution of cellulose and hemicellulose.
Moreover, the content of alkali metals and chlorine in biomass is
much higher than that of coal (Zhang et al., 2018a; Zeng et al., 2016).
Alkali metals and chlorine can easily form PM1 (particulate matter with
aerodynamic diameters of ≤1 µm) by gas phase reaction, homogeneous
nucleation, or heterogeneous condensation during biomass combustion,
causing problems such as agglomeration, slagging and corrosion in the
equipment, or releasing discharge into the atmosphere, which poses
serious harm to the environment and human body (Wang et al., 2018;
Brassard et al., 2014). The research about the release and

⁎
Corresponding author.
E-mail address: thyang@sau.edu.cn (T. Yang).

https://doi.org/10.1016/j.biortech.2019.01.032
Received 13 December 2018; Received in revised form 7 January 2019; Accepted 8 January 2019
Available online 09 January 2019
0960-8524/ © 2019 Elsevier Ltd. All rights reserved.
X. Kai et al. Bioresource Technology 278 (2019) 1–8

transformation characteristics of K and Cl during biomass torrefaction

and mild pyrolysis investigated by Chen et al. (2016) indicated that the
torrefaction pretreatment of biomass results in the release and trans-
formation of a considerable amount of alkali metal and chlorine.
However, the effect of torrefaction on the emission of PMs during
combustion is still unclear. Yani et al. (2015) compared the emission
behaviour of inorganic PM10 from the combustion of biomass by tor-
refying mallee leaves at 220–280 °C, and found that the combustion of
torrefied biomass results in a considerable reduction in PM1 and a
significant increase in PM1−10 compared with that of raw biomass.
However, Hu et al. (2018) proposed that under low temperature heat
pretreatment conditions, as the heat treatment temperature increased,
the PM1 emission of upgraded biomass combustion increased, reaching
a maximum at 500 °C. The emission behaviour of PM1 during co-com-
bustion of torrefied biomass and coal studied by Li et al. (2018) in-
dicated that the emission of PM0.3 reduced under two different mixing
ratios and torrefaction pretreatment resulted in a higher reduction ratio
of PM0.3 during the co-combustion of biomass and coal. Further, Han
et al. (2018) reported that the co-combustion of coal and torrefied rice
husks produced less PM1, but produced more PM1-10 than that from co-
combustion of coal and raw rice husks. These previous studies have
contributed considerably to the understanding of the effects of torre-
faction pretreatment on biomass. However, most emphasised on bio-
Fig. 1. Schematic diagram of the combustion system. 1. Screw feeder, 2. Air
mass itself, and studies on the role of torrefaction in the components of
compressor, 3. Flowmeter, 4 Temperature controller, 5. U type ash bucket, 6,
biomass and emission characteristics of particulate matters during Sampling tube, 7. Cyclone, 8. Bipolar diluter, 9. Air compressor, 10. Dryer, 11.
subsequent biomass combustion are scarce. ELPI+, 12. Vacuum pump. 13. Computer.
Hence, this paper aims to study the effects of torrefaction on the
physical and chemical properties of biomass and emission character-
the reactor was cooled and the flow rate of the carrier gas remained
istics of particulate matters in the subsequent combustion of torrefied
constant until the sample temperature was cooled to as low as 150 °C.
biomass, focusing on the effect of torrefaction temperature on the
After the torrefaction was completed, the torrefied samples were cooled
particle size distribution, elemental composition and microstructure of
to room temperature and weighted for further analysis.
fine particulate matters produced by torrefied biomass. This work will
The combustion experiments were performed using a laboratory-
contribute to the better understanding of the formation mechanism of
scale drop tube furnace system and the behaviour of PM emission from
PM10 in the combustion process of torrefied biomass and provide a
biomass combustion was studied with the new electric low-pressure
theoretical reference for industrial biomass combustion.
impactor (ELPI+), as shown in Fig. 1. The whole system primarily in-
cludes a spiral feeder, combustion chamber, temperature control
2. Material and methods
system, air supply system, and particulate sampling system. The com-
bustion chamber is composed of a high-temperature resistant gas-
2.1. Materials
smelting quartz tube and a heating element silicon carbide rod. The
feeding rate was approximately 15 g/min and the furnace temperature
The sample of RS used in this experiment was collected from the
was maintained at 850 °C controlled by the temperature of the control
suburb of Shenyang, China. The sample was pulverised, ground, and
system. The combustion gas flow is approximately 62.75 L/min with
sieved to a size less than 150 µm, and subsequently stored in a de-
air. Particulate matters were collected by aluminium foil and Whatman
siccator at room temperature for further use. HF, HNO3, H2O2, H2SO4,
polycarbonate filter. The ELPI+ classified the particulate matters in the
C19H42BrN (CTAB), and acetone used in the experiment were of ex-
range of 0.006–10 μm into 14 grades and measured the particle size
cellent grade supplied by Sinopharm Chemical Reagent Co., Ltd. China.
distribution (PSD) online. To ascertain the experimental quality, each
The water used in this study was deionised water purchased from
test was repeated more than thrice and the average was recorded.
Kermel Chemical Reagent Co., Ltd. in Tianjin, China.

2.2. Reaction system 2.3. Analytical methods

Torrefaction was conducted in a bench-scale nitrogen reactor of Solid and energy yields are the basis for measuring the feasibility
dimensions 450 × 400 × 400 mm. The reaction apparatus primarily and economics of torrefaction pretreatment for upgrading biomass fuels
consisted of a nitrogen cylinder ensuring an inert atmosphere, a rota- in industrial applications. The solid and energy yields of torrefied RS
meter controlling the nitrogen flow rate, a reactor using nitrogen oven were calculated based on the dry mass of RS defined as follows:
(HOC-DH45BF, China), a temperature controller, and a product gas
Mt
treatment unit for cleaning the exhaust gas. The torrefaction tempera- Solidyield(%) = × 100%
Mr (1)
tures preset at 200, 225, 250, 275 and 300 °C, and four different
durations of 10, 30, 50 and 70 min were considered to evaluate the HHVt × Mt
influence of torrefaction temperature and duration on the performance Energyyield(%) = × 100%
HHVr × Mr (2)
of torrefied RS. Prior to performing the experiments, the reactor was
heated up to the preset temperature with nitrogen at 20 L/min and was where Mr and Mt represent the masses (g) of the raw and torrefied RS,
maintained constant for 5 min. A thin layer of biomass particles loaded respectively; HHVr and HHVt represent the high heating values (HHVs)
in the porcelain ark was quickly placed into the centre of the reactor, (MJ/kg) of the raw and torrefied RS, respectively.
and the timing device was turned on simultaneously (reaction time is The proximate, ultimate, and HHV analysis results of the RS were
accurate to the second). When the pre-selected duration was reached, determined by an industrial analyser (5E-MAG6600B, China), a CHNS/

2
X. Kai et al. Bioresource Technology 278 (2019) 1–8

O elemental analyser (A3000 CHNS/O, Italy), and an oxygen bomb Table 1

calorimeter (5E-AC/PT, China), respectively. The FIWE 6 fibro-metre Chemical composition of RS obtained under different torrefaction temperatures
systems with the Van Soest cellulose content determination method for 30 min.
were used for fibre analyses, including hemicellulose, cellulose, and Raw 200 °C 225 °C 250 °C 275 °C 300 °C
acid-insoluble lignin. Fourier transform infrared (FTIR) analysis was
performed on an FTIR spectrophotometer (Thermo Scientific Nicolet Proximate analysis (wt %, air dry basis)
M 4.35 1.89 1.87 1.80 1.75 1.73
iS50, USA) to identify the distribution of functional groups in raw and
A 9.23 9.58 9.75 9.97 10.79 12.69
torrefied RS in the range of 4000–500 cm−1. The microstructures of raw V 74.86 75.20 74.84 73.83 71.33 66.42
and torrefied RS were examined using field emission scanning electron FCcd 11.56 13.33 13.54 14.40 16.13 19.16
microscopy (SEM, ULTRA PLUS, Germany). The raw and torrefied RS Proximate analysis (wt %, dry basis)
were digested with a mixture of HNO3, HF, and H2O2 in a microwave C 42.57 45.06 45.25 46.12 49.02 50.94
digestion apparatus, and analysed by inductively coupled plasma-op- H 5.84 5.46 5.43 5.39 5.16 4.90
tical emission spectrometry (ICP-OES, Perkin Elmer Optima 8300, N 2.13 2.60 3.56 4.08 5.20 5.46
S 0.13 0.10 0.10 0.15 0.16 0.16
America) to measure the concentrations of alkali metal (K and Na) and Ocd 49.33 46.77 45.65 44.26 40.46 38.55
selected inorganic mineral elements. The content of Cl in the raw and
Chemical composition analysis (wt %, dry basis)
torrefied RS was determined by high-temperature combustion hydro-
Hemicellulose 25.11 26.55 25.75 24.27 13.56 3.96
lysis-potentiometric titration according to the national standard Cellulose 35.32 35.82 37.28 39.57 42.48 38.99
“Determination of Chlorine in Solid Biofuels” (GB/T 30729-2014). The Lignin 12.20 12.68 13.06 13.57 14.78 16.16
particulate matter collected on the substrates was analysed by scanning Contents of inorganic elemental (wt %, dry basis)
electron microscopy–electron dispersive X-ray spectroscopy (SEM-EDS, K 1.131 1.097 1.113 1.134 1.151 1.117
Nova 450 Nano SEM, America) to study the morphologies and ele- Na 0.540 0.486 0.453 0.447 0.473 0.099
mental compositions. Cl 0.630 0.662 0.671 0.634 0.661 0.662
Ca 0.120 0.123 0.128 0.125 0.146 0.159
Mg 0.068 0.070 0.072 0.075 0.078 0.084
3. Results and discussion Si 2.082 2.308 2.500 2.523 2.635 2.693

cd
3.1. Solid and energy yields of torrefied RS Calculated by difference.

The effects of torrefaction temperature and duration on the solid
yield, energy yield and HHV of the RS are shown in Fig. 2. It can be seen
from Fig. 2(a) that the solid yield was reduced from 94.35% to 88.66%
in the low torrefaction temperature range of 200–250 °C, whereas a
remarkable decrease from 88.66% to 70.49% was observed in the high
temperature range of 250–300 °C. The effect of torrefaction tempera-
ture on the solid yield of RS was enhanced gradually with increasing
temperature. This was primarily attributed to an increase in the release
of moisture and volatiles with increasing temperature. A small increase
in energy yield was observed at 225 °C. When the temperature was
greater than 225 °C, the energy yield was reduced from 98.52% to
84.41% in the torrefaction temperature range of 225–300 °C, and the
degree of decrease in the energy yield was increased with the increase
in temperature. Owing to the degree of increase in HHV increasing with
the increase of temperature, the energy yield decreased slowly com-
pared with the solid yield. As shown in Fig. 2(b), with the increase in
duration from 10 to 70 min, the solid and energy yields of torrefied RS
were decreased by 5.35% and 3.01%, respectively, and the degree of
decrease was reduced gradually. The HHV of the RS increased sig-
nificantly at 30 min, as the duration was prolonged further, the increase
of the HHV began to decline. It is noteworthy that the effect of torre-
faction temperature on the solid yield, energy yield, and HHV of RS are
more prominent than that of duration.
3.2. Chemical components of torrefied RS
The proximate and ultimate analyses of the RS obtained under
different torrefaction temperatures are presented in Table 1. As shown,
the moisture content of raw RS was reduced to 1.89% at 200 °C;
whereas, further increasing the torrefaction temperature had little ef-
fect on it. It is noteworthy that the significant decrease in moisture
content led to an increase in the content of other components at 200 °C.
The torrefaction temperature demonstrated a notable effect on the vo-
latile content of RS. The volatile content was decreased from 75.20% at
200 °C to 66.42% at 300 °C, and the decrease was enhanced with in-
creasing torrefaction temperature, resulting in a gradual increase in ash
content and fixed carbon content of torrefied RS, which were increased
by 3.46% and 7.6%, respectively. The results of the ultimate analysis
indicated that carbon content increased gradually, and the hydrogen
and oxygen content decreased gradually with increasing torrefaction
temperature. Especially when the temperature was greater than 250 °C,
the temperature demonstrated a more evident impact on them. In ad-
dition, Table 2 summarises that the results of the proximate and ulti-
mate analyses about torrefied RS obtained at different durations ex-
hibited the similar trend compared with that obtained at different
torrefaction temperatures, but the influence of duration was slight.
Moreover, Tables 1 and 2 summarise the contents of hemicellulose,

Fig. 2. Solid and energy yields of torrefied RS. (a) Effect of torrefaction temperature, duration 30 = min, (b) Effect of duration, torrefaction temperature = 250 °C.

3
X. Kai et al. Bioresource Technology 278 (2019) 1–8

Table 2 loss of hemicellulose below 250 °C, and its significantly decomposition
Chemical composition of torrefied RS obtained under different torrefaction at 300 °C, thereby resulting in the weight loss of RS during torrefaction.
durations at 250 °C. In addition, the decarboxylation reaction of hemicellulose-released
10 min 30 min 50 min 70 min oxygen-containing compounds (Zhang et al., 2016), resulted in a de-
crease in oxygen content in torrefied RS. This was consistent with the
Proximate analysis (wt %, air dry basis) results of the elemental analysis. Compared with hemicellulose, cellu-
M 1.83 1.80 1.65 1.53
lose is a linear macromolecular polysaccharide consisting of long-chain
A 9.62 9.97 10.15 10.58
V 75.24 73.83 73.56 73.05 glucose units linked by β-1,4-glycosidic bonds (Wang et al., 2017b) that
FCcd 13.31 14.40 14.64 14.84 tended to decompose at higher temperatures. Thus, the mass loss of
Proximate analysis (wt %, dry basis) cellulose during torrefaction was much lower than that of hemi-
C 45.57 46.12 46.69 46.62 cellulose, and the relative content of cellulose increased when torre-
H 5.44 5.39 5.29 5.35 faction temperature increased, whereas cellulose was significantly de-
N 4.03 4.08 4.48 5.06 composed when the torrefaction temperature reached 300 °C, thus
S 0.14 0.15 0.13 0.13
Ocd 44.82 44.26 43.40 42.85
causing the solid yield to be reduced significantly at 300 °C. Lignin
demonstrated the better thermal stability and decomposed slowly
Chemical composition analysis (wt %, dry basis)
during torrefaction. The relative content of lignin was increased from
Hemicellulose 24.66 24.27 21.96 20.43
Cellulose 38.34 39.57 40.26 40.53 12.68% at 200 °C to 16.16% at 300 °C because of the decomposition of a
Lignin 13.12 13.57 13.66 13.75 large amount of hemicellulose. As listed in Table 2, the effect of tor-
Contents of inorganic elemental (wt %, dry basis) refaction duration on the three components was not evident. When the
K 1.107 1.134 1.143 1.152 torrefaction temperature was 250 °C and the duration was extended
Na 0.459 0.447 0.409 0.259 from 10 to 70 min, the content of hemicellulose was reduced from
Cl 0.610 0.634 0.635 0.636 24.66% to 22.43%, and the content of cellulose and lignin was in-
Ca 0.125 0.125 0.130 0.133
Mg 0.078 0.075 0.074 0.077
creased slowly.
Si 2.504 2.523 2.571 2.583 In addition to hemicellulose, cellulose, and lignin, biomass also in-
cludes a small number of inorganic mineral elements that, although low
cd
Calculated by difference. in content, can directly affect the formation of PMs. As presented in
Tables 1 and 2, the contents of alkali metal K and anion Cl in RS were
Table 3 high, and they evaporated and condensed easily to dominate the for-
Release of Cl and K of torrefied RS at different temperature. mation of PM1 during biomass combustion (Wang et al., 2018). As the
200 °C 225 °C 250 °C 275 °C 300 °C torrefaction degree increased, the alkali metal K content increased, but
decreased rapidly at 300 °C. In addition, the relative contents of Cl and
Cl-release ratio (%) 0.85 1.14 10.78 14.11 25.93 some heat resisting inorganic elements such as Mg, Ca and Si in tor-
K-release ratio (%) 8.51 8.64 11.12 16.72 30.38
refied RS were increased.
molar ratio (Cl-release/K-release) 0.061 0.08 0.594 0.516 0.522
To further illustrate the release behaviour of Cl and K and their
relationships during RS torrefaction, the release behaviour of Cl and K
cellulose and lignin in raw and torrefied RS. As listed in Table 1, the under different torrefaction temperatures is presented in Table 3. The
content of hemicellulose relative to the weight of torrefied RS was release ratio of K or Cl during torrefaction was calculated by mass
decreased from 26.55% to 3.96% with the increase in torrefaction conservation, which was calculated according to following equation:
temperature from 200 °C to 300 °C, and the degree of decrease in- mCl / K − r − mCl / K − t × Y
creases. Hemicellulose consists of short-chain heteropolysaccharides Cl/K_release(%) = × 100%
mCl / K − r (3)
and exhibits an amorphous and branched structure (Wang et al.,
2017b); thereby, hemicellulose degraded first during torrefaction. The where, mCl/K−r and mCl/K−t are the Cl or K concentrations of raw and
maximum weight loss of hemicellulose focused at the range of torrefied RS on the dry basis, respectively; Y is the solid yield of tor-
185–325 °C, and two weight loss peaks appeared at approximately refied RS on the dry basis.
233 °C and 285 °C (Ma et al., 2015), thus explaining the slow weight As listed in Table 3, when the torrefaction duration was fixed at

Fig. 3. (a) Mass-based particle size distribution (PSD) of PM10 from RS combustion obtained at different torrefaction temperatures and (b) PM yields from RS
combustion obtained at different torrefaction temperatures.

4
X. Kai et al.
Fig. 4. Elemental mass size distribution of K, Na, Cl, S, Mg, Ca, and Si in PM10 from the combustion of: (a) raw RS, (b) torrefied RS obtained at 200 °C, (c) torrefied RS
obtained at 250 °C, (d) torrefied RS obtained at 300 °C.
30 min, the release ratio of Cl in torrefied RS was increased gradually
from 0.85% to 25.93% as the torrefaction temperature was increased
from 200 °C to 300 °C, and a remarkable increase in Cl release was
observed as the temperature reached 250 °C. Cl is primarily present in
the form of water-soluble inorganic salt KCl in biomass (Saidur et al.,
2011). Cl was released primarily as gaseous HCl and CH3Cl formed
through ion-exchange reactions between KCl and carboxyl groups or
other oxygen-containing functional groups in the organic matrix during
torrefaction. Studies had shown that the release of CH3Cl began to in-
crease significantly at 250 °C (Hamilton et al., 2003), and that HCl
began to form at approximately 230 °C (Wu et al., 2013), thus ex-
plaining the reason for the significant increase in Cl release at 250 °C.
The release ratio of K was increased gradually from 8.51% at 200 °C to
30.38% at 300 °C, and the degree of increase in the release ratio also
increased with increasing torrefaction temperature. The molar ratio of
5
Bioresource Technology 278 (2019) 1–8
K to Cl in raw RS was 1.6, and K was primarily present in the form of
water-soluble inorganic salts KCl, K2SO4 and K2Si2O5 in the straw (Wei
et al., 2005; Tchoffor et al., 2013), where the K atom in KCl would
replace the H functional group in the carboxyl group to form organi-
cally associated K retained in torrefied RS. The molar release of Cl and K
was unbalanced in that the molar release of K was greater than that of
Cl. It follows that other forms of K-containing compounds were pri-
marily converted into gas phase K during torrefaction, in addition to the
decomposition of KCl. According to the results of fibre component
analysis, hemicellulose began to decompose significantly at 250 °C.
Therefore, the –H functional group and oxygen-containing functional
group in organic volatiles promoted the release of Cl and K during
torrefaction. Conversely, Cl and K ions can form new hydrogen bonds
with carboxyl groups and hydroxyl groups on the branches of organic
molecules (such as hemicellulose), thus destroying intra- and
X. Kai et al.
intermolecular hydrogen bonds, thereby accelerating the decomposi-
tion of the organic matrix.
3.3. Organic functional groups of torrefied RS
The FTIR spectra of the torrefied RS at different temperatures and
durations exhibited similar peak assignments, indicating that the tor-
refied RS contained the same functional groups. The band at
3600–3050 cm−1 represented the –OH stretching vibrations associated
with H2O. With increasing temperature, the peak intensity of –OH was
weakened, which was primarily owing to hydroxyl cleavage and in-
tramolecular dehydration reaction in cellulose and hemicellulose (Yang
et al., 2016; Xin et al., 2018). The absorption peaks at 1606 and
1713 cm−1 were caused by C]O stretching vibrations associated with
carboxylic acid, aldehydes, and ketones. The C]O group strength of
torrefied RS obtained with high temperatures was not weakened, in-
dicating that hemicellulose and cellulose decarboxylation, carbonyl and
ring C]O radicals to generate a series of aldehydes, ketones, carboxylic
acid and other tar substances may be adsorbed onto torrefied RS. The
strong absorption observed at 1032 cm−1 was assigned to the C–O
stretching vibration of carboxyl-containing organics. The C–O
stretching absorption band faded in intensity with increasing torrefac-
tion temperature from 200 °C to 300 °C, which may be attributed to the
hemicellulose and cellulose undergoing pyrolysis reactions (Zhang
et al., 2016; Xin et al., 2015). The band between 900 and 600 cm−1 was
primarily the C–H bending vibration of the aromatic rings and their
derivatives in lignin. The vibration was weakened with increasing
temperature because of the ring opening, indicating that the degree of
carbonisation of torrefied RS increased.
The FTIR spectra trend of the torrefied RS obtained under different
durations was consistent with that obtained under different tempera-
tures, both exhibited similar peak assignments, indicating that the
torrefied RS contained the same functional groups, and the trend of
change was the same. This was consistent with the results of the fibre
composition in Section 3.2.
The FTIR spectra of the torrefied RS contained the same functional
groups. Torrefaction decreased the oxygen-containing functional
groups (–OH and C–O); whereas, the intensity of C]O, C–H and C]C
indicated marginal change, where C]O stretching vibrations were as-
sociated with aldehydes, ketones, and acids adsorbed onto torrefied RS.
3.4. Morphological structures of torrefied RS
To gain deeper insight about the impact of torrefaction temperature
and duration on the RS structure, SEM was used for observing the
surface morphology of the torrefied RS at a magnification of 2000×.
The test samples were placed in a sample chamber after being sprayed
with gold under vacuum and subjected to scanning after vacuuming.
Numerous impurities could be clearly observed on the surface of
raw RS. However, after undergoing torrefaction at 200 °C, the im-
purities were consumed considerably and the surface became smoother
with a small number of microporous structures, caused by the dehy-
dration and degradation of hemicellulose. The number of microporous
on the surface of torrefied RS increased as the torrefaction temperature
increased. The damage or pits in the surface structures of torrefied RS
obtained over 250 °C was exhibited and the structures converted gra-
dually from a full form to a loose form; this trend became increasingly
evident with increasing torrefaction temperature. Moreover, when the
torrefaction temperature was increased to 300 °C, the surface structure
was accompanied by fracture and collapse, and the porous structure
disappeared. With the extension of torrefaction duration, the surface
structures of the torrefied RS were broken severely and the number of
microporous increased gradually. In a word, when increasing the tor-
refaction temperature or prolonging the torrefaction duration, the tor-
refied RS appear looser and more brittle; thus, improving the grind-
ability of biomass.
6
Bioresource Technology 278 (2019) 1–8
3.5. Mass particle size distribution and yields of PM10 from torrefied RS
The emission behaviour of particulate matters from the combustion
of raw and torrefied RS obtained at different torrefaction temperatures
is depicted in Fig. 3. As shown in Fig. 3(a), the mass-based particle size
distribution (PSD) of PM10 from the combustion of both raw and tor-
refied RS demonstrated a similar unimodal distribution with a peak at
0.6 μm. Clearly, the observed PSDs all primarily consisted of PM0.1–10
(i.e., PM with an aerodynamic diameter of 0.1–10 μm), which can be
discussed by dividing with a fine mode < 1 μm (PM1) and a coarse
mode < 1 μm (PM1−10) because of their different formation mechan-
isms. The mass-based PSDs of PM1 generated from the torrefied RS
appeared to be higher than those from raw RS, and increasing the
torrefaction temperature from 200 to 300 °C intensified this trend. The
mass-based PSDs of PM1–10 generated from torrefied RS increased sig-
nificantly as the torrefaction temperature increased. Fig. 3(b) shows
much higher yields of PM1–10 compared with that of PM1 during the
combustion of both raw and torrefied RS. Noted that the torrefied RS
produced more PM1–10 than raw RS, but the yields of PM1 were similar.
When the torrefaction temperature was increased from 200 to 300 °C,
the yields of PM1 and PM1–10 were enhanced by 40% and 70%, re-
spectively, indicating that torrefaction tended to enhance PM1–10
emissions but impacted less on PM1 emissions.
It has been shown in previous research that the PM1 from biomass
combustion is primarily formed through vaporisation-condensation,
while PM1–10 is formed principally by char fragmentation, evaporation
of minerals, coalescence of included minerals and fragmentation of
excluded minerals (Han et al., 2018; Christensen et al., 1998). The
content of Cl and K in the RS listed in Table 1 is high. In a high-tem-
perature environment, the K released in biomass can be captured by the
aluminosilicate oxides to form a solid phase alkali metal aluminosilicate
or combined with Cl to form a vapour phase KCl vapour (Han et al.,
2018). The higher concentration of K-containing vapour species was the
primary cause of higher PM1 emission. The mineral vapour underwent a
series of gas phase reactions, homogeneous nucleation, or hetero-
geneous condensation on the existing finer particle surfaces to form
larger particles. As listed in Table 1, although the torrefaction released
some of the Cl and K in the RS, the relative contents of Cl and K in
torrefied RS was not reduced; hence, the PM1 emissions from the tor-
refied RS increased instead of decreasing. The PM1–10 yield from the
combustion of RS torrefied at 300 °C was approximately 1.8 times that
of the raw RS. This is primarily because the torrefaction process in-
creased the ash and microporous structures in the biomass, thus, ren-
dering the biomass loose and brittle, thereby causing the biomass char
to break easily to form PM1–10 during combustion. Meanwhile, the in-
crease in PM1–10 yield with torrefaction temperature indicated that the
mineral and finer particles coalesced more intensely during the com-
bustion of RS obtained at higher torrefaction temperatures, thereby,
leading to the formation of PM1–10.
3.6. Elemental compositions and morphologies of PM10 from torrefied RS
Fig. 4 shows the key elemental composition of PM10 collected in
each stage from RS combustion. As shown, PM1 from the combustion of
raw and torrefied RS was primarily formed by vaporised species in-
cluding K, Na, Cl, and S with K and Cl predominating, while PM1–10 was
primarily formed by refractory elements including Mg, Ca and Si, such
as silicate, and contained a certain amount of K, S, and Cl. This further
proved that PM1 produced by biomass combustion was primarily
formed by the homogeneous nucleation and heterogeneous condensa-
tion of volatile alkali metal salt vapour, primarily composed of alkali
chlorites and a small number sulphates; whereas, PM1–10 was primarily
formed by inorganic mineral breakage, and the collisional coalescence
and heterogeneous condensation of alkali metal salts.
Furthermore, the elemental composition other than the S of PM1
emitted from the combustion of torrefied RS obtained at 200 °C was
X. Kai et al.
similar to that of the raw RS, while the mass fraction of S was decreased
significantly. The significant decrease in the S content inhibited the
formation of sulphates by S with Na and K, thus, reducing the mass
fraction of PM1. With the further increase of torrefaction temperature,
the mass fraction of other elements in the fine particulate matters
produced by the torrefied RS burning were increased, and only the mass
fraction of Na was decreased. It is noteworthy that the mass con-
centration of the primary elements K and Cl in PM1, which was much
greater than that of Na, increased with increasing torrefaction tem-
perature, thereby increasing the mass fraction of PM1 produced by
torrefied RS combustion. As for PM1–10, Ca, Mg and Si were enriched in
PM1–10 and their mass concentrations of increased gradually with in-
creasing torrefaction temperature. These species were the essential
mineral composition of biomass ash, and were resistant to high tem-
perature and difficult to remove during torrefaction; therefore, they
collided with each other during the combustion of torrefied RS, re-
sulting in the formation of silicates and/or aluminosilicates and the
subsequent formation of PM1–10 by coalescence. It was also possible
that the direct release of organically bound Ca and Mg, and the sub-
sequent melt sintering also contributed to the formation of PM1–10.
To further clarify the difference between PM1 and PM1–10 produced
by the combustion of torrefied RS, the microscopic morphologies and
elemental compositions of the particular matters were analysed by
SEM–EDS. It can be observed that PM1 was agglomerated by regular-
shaped cubic crystals that were representative structures of KCl. PM1–10
consisted primarily of irregular flocculent particles, smooth spheres of
molten material, and regular hexagonal crystal structures; on the sur-
face of the spheres, a certain number of irregularly shaped substances
can be observed. The highly different composition and microstructure
between PM1 and PM1–10 were attributed to different formation me-
chanisms. Irregular flocculent particles may be attributed to the broken
and melting of minerals in the char fragments during the combustion of
torrefied RS. In addition, the results obtained by EDS surface scanning
indicated that the smooth spheres represented the K4SiO3 structure
primarily, and the irregularly shaped substance adsorbed on the surface
was ultrafine-mode particles condensed by gaseous KCl vapours, and
the hexagonal crystal structures were also of KCl structure. This further
confirmed that a certain amount of K and Cl existed in the PM1–10
produced by the combustion of torrefied RS, i.e., the torrefaction pre-
treatment can promote the heterogeneous condensation of KCl vapour
to form larger particles.
4. Conclusions
Torrefaction improved the HHV of RS, but decreased the solid and
energy yield. And torrefaction temperature (200–300 °C) had an ob-
vious influence on RS compared to duration (10–70 min). Release ratio
of Cl and K increased to 25.93% and 30.38% at 300 °C, respectively.
However, the removal of Cl and K did not reduce the PM1 emissions.
The mass-based PSDs of PM1 and PM1–10 increased with the torrefaction
temperature, and the yields of PM1–10 were much higher than those of
PM1. Finally, the torrefaction pretreatment could promote the hetero-
geneous condensation of KCl vapour to form PM1–10.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (51576135) and Education Department Project of
Liaoning Province (L201736).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.biortech.2019.01.032.
7
Bioresource Technology 278 (2019) 1–8
References
Brassard, P., Palacios, J.H., Godbout, S., Bussières, D., Lagacéc, R., Larouche, J.P.,
Pelletier, F., 2014. Comparison of the gaseous and particulate matter emissions from
the combustion of agricultural and forest biomasses. Bioresour. Technol. 155,
300–306.
Chen, H., Chen, X., Qiao, Z., Liu, H., 2016. Release and transformation characteristics of K
and Cl during straw torrefaction and mild pyrolysis. Fuel 167, 31–39.
Chen, H., Chen, X., Qin, Y., Qiao, Z., Wei, J., Liu, H., 2017. Effect of torrefaction on the
properties of rice straw high temperature pyrolysis char: pore structure, aromaticity
and gasification activity. Bioresour. Technol. 228, 241–249.
Chen, D., Gao, A., Ma, Z., Chen, D., Gao, A., Ma, Z., Fei, D., Chang, Y., Shen, C., 2018. In-
depth study of rice husk torrefaction: characterization of solid, liquid and gaseous
products, oxygen migration and energy yield. Bioresour. Technol. 253, 148–153.
Christensen, K.A., Stenholm, M., Livbjerg, H., 1998. The formation of submicron aerosol
particles, HCl and SO2 in straw-fired boilers. J. Aerosol. Sci. 29, 421–444.
Correia, R., Gonçalves, M., Nobre, C., Mendes, B., 2018. Impact of torrefaction and low-
temperature carbonization on the properties of biomass wastes from Arundo donax L.
and Phoenix canariensis. Bioresour. Technol. 223, 210–218.
Dai, G., Zou, Q., Wang, S., Zhao, Y., Zhu, L., Huang, Q., 2018. Effect of torrefaction on the
structure and pyrolysis behavior of lignin. Energy Fuel. 32, 4160–4166.
Gao, X., Chen, Y., Sheng, C., Wu, H., 2016. Interaction between sodium vapor and reactor
wall during biomass combustion and its influence on measurement of particulate
matter emission. Fuel 165, 260–263.
Hamilton, J.T., Mcroberts, W.C., Keppler, F., Kalin, R.M., Harper, D.B., 2003. Chloride
methylation by plant pectin: an efficient environmentally significant process. Science
301, 206–209.
Han, J., Yu, D., Yu, X., Liu, F., Wu, J., Zeng, X., Yu, G., Xu, M., 2018. Effect of the
torrefaction on the emission of PM10 from combustion of rice husk and its blends
with a lignite. Proc. Combust. Inst. https://doi.org/10.1016/j.proci.2018.07.011.
Hu, Z., Wang, X., Adeosun, A., Ruan, R., Tan, H., 2018. Aggravated fine particulate matter
emissions from heating-upgraded biomass and biochar combustion: the effect of
pretreatment temperature. Fuel Process. Technol. 171, 1–9.
Kai, X., Li, R., Yang, T., Shen, S., Ji, Q., Zhang, T., 2017. Study on the co-pyrolysis of rice
straw and high density polyethylene blends using TG-FTIR-MS. Energy Convers.
Manage. 146, 20–33.
Li, C., Wen, C., Wang, W., Wang, W., Chen, H., Yu, D., Xu, M., 2018. Reduction effect of
co-firing of torrefied straw and bituminous coal on PM1 emission under both air and
oxyfuel atmosphere. Proc. Combust. Inst. https://doi.org/10.1016/j.proci.2018.07.
012.
Ma, Z., Chen, D., Gu, J., Bao, B., Zhang, Q., 2015. Determination of pyrolysis char-
acteristics and kinetics of palm kernel shell using TGA–FTIR and model-free integral
methods. Energy Convers. Manage. 89, 251–259.
Mei, Y., Liu, R., Yang, Q., Yang, H., Shao, J., Draper, C., Zhang, S., Chen, H., 2015.
Torrefaction of cedarwood in a pilot scale rotary kiln and the influence of industrial
flue gas. Bioresour. Technol. 177, 355–360.
Mi, B., Liu, Z., Hu, W., Wei, P., Jiang, Z., Fei, B., 2016. Investigating pyrolysis and
combustion characteristics of torrefied bamboo, torrefied wood and their blends.
Bioresour. Technol. 209, 50–55.
Saidur, R., Abdelaziz, E.A., Demirbas, A., Hossain, M.S., Mekhilef, S., 2011. A review on
biomass as a fuel for boilers. Renew. Sustain. Energy Rev. 15, 2262–2289.
Sheldon, R.A., 2014. ChemInform Abstract: green and sustainable manufacture of che-
micals from biomass: state of the art. Green Chem. 45, 950–963.
Song, X., Yang, Y., Zhang, M., Zhang, K., Wang, D., 2018. Ultrasonic pelleting of torrefied
lignocellulosic biomass for bioenergy production. Renew. Energy 129, 56–62.
Sukiran, M.A., Abnisa, F., Wan Daud, W.M.A., Bakar, N.A., Loh, S.K., 2017. A review of
torrefaction of oil palm solid wastes for biofuel production. Energy Convers. Manage.
149, 101–120.
Tchoffor, P.A., Davidsson, K.O., Thunman, H., 2013. Transformation and release of po-
tassium, chlorine, and sulfur from wheat straw under conditions relevant to dual
fluidized bed gasification. Energy Fuel 27, 7510–7520.
Uemura, Y., Matsumoto, R., Saadon, S., Matsumura, Y., 2015. A study on torrefaction of
laminaria japonica. Fuel Process. Technol. 138, 133–138.
Valix, M., Katyal, S., Cheung, W.H., 2017. Combustion of thermochemically torrefied
sugar cane bagasse. Bioresour. Technol. 223, 202–209.
Wang, S., Dai, G., Ru, B., Zhao, Y., Wang, X., Zhou, J., Luo, Z., Cen, K., 2016. Effects of
torrefaction on hemicellulose structural characteristics and pyrolysis behaviors.
Bioresour. Technol. 218, 1106–1114.
Wang, S., Dai, G., Ru, B., Zhao, Y., Wang, X., Xiao, G., Luo, Z., 2017a. Influence of tor-
refaction on the characteristics and pyrolysis behavior of cellulose. Energy 120,
864–871.
Wang, S., Dai, G., Yang, H., Luo, Z., 2017b. Lignocellulosic biomass pyrolysis mechanism:
a state-of-the-art review. Prog. Energy Combust. Sci. 62, 33–86.
Wang, X., Hu, Z., Adeosun, A., Ruan, R., Li, S., Tan, H., 2018. Particulate matter emission
and K/S/Cl transformation during biomass combustion in an entrained flow reactor.
J. Energy Inst. 91, 835–844.
Wei, X., Schnell, U., Hein, K.R.G., 2005. Behaviour of gaseous chlorine and alkali metals
during biomass thermal utilization. Fuel 84, 841–848.
Wu, P., Yu, C., Bai, J., Li, L., Huang, F., 2013. Mechanism study of chlorine release during
biomass pyrolysis. Proc. CSEE 33, 75–81.
Xia, S., Xiao, H., Liu, M., Chen, Y., Yang, H., Chen, H., 2018. Pyrolysis behavior and
economics analysis of the biomass pyrolytic polygeneration of forest farming waste.
Bioresour. Technol. 270, 189–197.
Xin, S., Yang, H., Chen, Y., Yang, M., Chen, L., Wang, X., Chen, H., 2015. Chemical
structure evolution of char during the pyrolysis of cellulose. J. Anal. Appl. Pyrol. 116,
X. Kai et al.
263–271.
Xin, S., Mi, T., Liu, X., Huang, F., 2018. Effect of torrefaction on the pyrolysis char-
acteristics of high moisture herbaceous residues. Energy 152, 586–593.
Xu, X., Tu, R., Sun, Y., Li, Z., Jiang, E., 2018. Influence of biomass pretreatment on up-
grading of bio-oil: comparison of dry and hydrothermal torrefaction. Bioresour.
Technol. 262, 261–270.
Yang, T., Jie, Y., Li, B., Kai, X., Yan, Z., Li, R., 2016. Catalytic hydrodeoxygenation of
crude bio-oil over an unsupported bimetallic dispersed catalyst in supercritical
ethanol. Fuel Process. Technol. 148, 19–27.
Yang, T., Wang, J., Li, B., Kai, X., Xing, W., Li, R., 2018. Behaviors of rice straw two-step
liquefaction with sub/supercritical ethanol in carbon dioxide atmosphere. Bioresour.
Technol. 258, 287–294.
Yani, S., Gao, X., Wu, H., 2015. Emission of inorganic PM10 from the combustion of
Bioresource Technology 278 (2019) 1–8
torrefied biomass under pulverized-fuel conditions. Energy Fuel 29, 800–807.
Zeng, X., Yu, D., Xiu, Y., Fan, B., Wu, J., Du, Y., Yu, X., Yao, H., Xu, M., 2016. Particulate
matter formation characteristics during zhundong coal and rice husk co-combustion.
Proc. CSEE 36, 4429–4435.
Zhang, R., Lei, K., Ye, B.Q., Cao, J., Liu, D., 2018a. Effects of alkali and alkaline earth
metal species on the combustion characteristics of single particles from pine sawdust
and bituminous coal. Bioresour. Technol. 268, 278–285.
Zhang, S., Su, Y., Xu, D., Zhu, S., Zhang, H., Liu, X., 2018b. Assessment of hydrothermal
carbonization and coupling washing with torrefaction of bamboo sawdust for biofuels
production. Bioresour. Technol. 258, 111–118.
Zhang, Y., Yao, A., Song, K., 2016. Torrefaction of cultivation residue of Auricularia
auricula-judae to obtain biochar with enhanced fuel properties. Bioresour. Technol.
206, 211–216.