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Emissions of SO 2, NO x, CO 2, and HCl from Co-firing of coals with raw and

torrefied biomass fuels

Article  in  Fuel · January 2018

DOI: 10.1016/j.fuel.2017.09.049

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 Fuel 211 (2018) 363–374

Contents lists available at ScienceDirect

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

Full Length Article

Emissions of SO2, NOx, CO2, and HCl from Co-firing of coals with raw and MARK
torrefied biomass fuels
⁎ ⁎
Emad Roknia, Xiaohan Renb,c, , Aidin Panahia, Yiannis A. Levendisa,
a
Mechanical and Industrial Engineering Department, Northeastern University, Boston, MA 02115, USA
b
Institute of Thermal Science and Technology, Shandong University, Jinan 250061, China
c
School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 150001, China

A R T I C L E I N F O A B S T R A C T

Keywords: This work examined acid gas emissions of sulfur dioxide, nitrogen oxide, carbon dioxide, and hydrogen chloride
Coal-biomass blends from co-firing biomass (corn straw and rice husk) with either a high-sulfur bituminous coal or a low-sulfur sub-
Raw and torrefied biomass bituminous coal. Pulverized neat coals, neat biomass, either raw or torrefied, and 50–50 wt% blends thereof
Pollutant emissions were introduced to a laboratory-scale electrically-heated drop-tube furnace (DTF), operated at a gas temperature
SO2
of 1350 K, and experienced high heating rates. Emissions from the combustion of the fuels in air were measured
NOx
at the furnace effluent. Coal particles were in the range of 75–90 µm and biomass particles in the range of
CO2
HCl 90–150 µm. Results revealed that blending of both coals with raw and torrefied biomass drastically reduced the
coal’s SO2 and NOx emission yields to values that were below those predicted by linear interpolation of the
corresponding emission yields of the two neat fuels. The SO2 emission yields from torrefied biomass were lower
than those of their raw biomass precursors due to their lower sulfur contents. Similarly to the emission yields, the
SO2 emission factors (based on the energy content of each sample) from the blends of coal with torrefied biomass
were also lower than the blends of coal with raw biomass. NOx emission yields from neat torrefied biomass were
mildly higher than those from raw biomass, as the latter had higher nitrogen content per unit mass. There was no
discernible trend in NOx emissions from the blends based on their nitrogen contents. HCl emission from torrefied
corn straw was lower than that from its raw precursor, as the former had a lower chlorine content. The HCl
emission yields from the blends of corn straw with coal were much higher than those from neat coal combustion.
Finally, the HCl emission yield from blends of the high-sulfur coal with corn straw were higher than those from
the blends of the same biomass with the low-sulfur coal.

1. Introduction and 12% was derived in biomass-based electricity generation systems

1.1. Bioenergy harvested from co-firing biomass with coal
Concerns about the environmental impact from using fossil fuels in
electricity generation have promoted the use of alternative renewable
sources of energy, such as solar, wind and biomass. Biomass is one of
the oldest sources of energy; it is derived from organic matter such as
agricultural crops, forest harvest residues, seaweed, herbaceous mate-
rials, and organic wastes. A reasonable option for biomass utilization is
co-firing with coal in conventional coal-fired boilers’ as such infra-
structure is already available and it only requires limited modifications
[1]. In recent years, bioenergy accounted for 10% (51 EJ) of the total
global energy supply which value was greater than any other renewable
source of energy [2]. About 50% of the total bioenergy was derived
from traditional use of biomass in wood stoves in developing countries,
[2]. Co-firing biomass with coal can be an economic option in power
generation, and its overall cost depends on the availability and the
proximity of the biomass feedstock to the power plant. Capital and
operational costs of co-firing are significantly lower than the cost of
neat biomass-fired power plants [3].
1.2. Environmental aspects of co-firing biomass and coal
1.2.1. Greenhouse gases emissions
Biomass may be considered as a nearly CO2-neutral fuel [4] as there
are still emissions related to its harvesting, transportation, pre-treat-
ment etc. Moreover, burning biomass prevents release of methane
(CH4) from decaying residues, which is important given that CH4 has a
21 times higher global warming potential (GWP) than CO2 [5]. In ad-
dition, the alkaline ashes of biomass may capture some of the CO2 gases

⁎
Corresponding authors.
E-mail addresses: xiaohan09126@gmail.com (X. Ren), y.levendis@neu.edu (Y.A. Levendis).

http://dx.doi.org/10.1016/j.fuel.2017.09.049
Received 7 June 2017; Received in revised form 1 September 2017; Accepted 13 September 2017
0016-2361/ © 2017 Elsevier Ltd. All rights reserved.
E. Rokni et al.
from the combustion event [5]. As storing biomass wastes also causes
anaerobic release of NH3, H2S, volatile organic acids, and other che-
micals, combusting the biomass helps prevent such emissions, which
has been reported by other researchers [6–29].
1.2.2. SO2 and NOx Emissions
Most biomass fuels contain little sulfur; therefore, their co-firing
with coal typically results in lower SO2 emissions [30]. NOx emissions
arise from atmospheric nitrogen and from fuel-bound nitrogen, which is
released during both the devolatilization and the char oxidation phases.
Volatile matter release from biomass combustion is higher than that
from coal, and during this phase volatilized tars shuttle fuel nitrogen to
the volatile matter flame [31]. Therein biomass-bound nitrogen forms
mostly NH3, rather than HCN which is typically formed by coal-bound
nitrogen, and this could help prevent the eventual formation of NOx in
flames [27–29,32]. A previous study on co-firing coal and rice husk
[33] reported that keeping the amount of coal the same and increasing
the amount of biomass in the blends decreased the NO emissions but
slightly increased the SO2 emissions. The reduction in NO was attrib-
uted to the lower terminal velocities of the rice husk particles than
those of the coal particles, due to their density difference [34]. This
caused the rice husk particles to burn earlier and to release volatile
gases, which reduced the amount of NO from coal oxidation via the
“reburning” mechanism [35,36]. Another study reported that co-firing
a bituminous coal with 10–20% straw (on an energy basis) in a
250 MWe coal boiler resulted in a net decrease in SO2 and NOx emis-
sions [37]. Therein, the lower sulfur content of the blended fuel and
higher sulfur retention in the ash were the main causes of the lower SO2
emissions. Moreover, while the nitrogen content of that blended fuel
was higher than the coal’s, a lower overall conversion of the fuel-N to
NO was reported as the main reason for the lower NO emission [37].
Another study [7] of co-firing coal with 60 wt% bagasse, wood chips,
sugarcane trash and coconut shell biomass also reported reductions of
SO2, NOx and suspended particulate matter (SPM). Furthermore, co-
firing a sub-bituminous coal with different types of biomass with
variable nitrogen contents, such as wood chips, sugarcane bagasse,
cotton stalk, and shea meal showed that their addition reduced the NOx
emissions of the coal [38]. In these and other studies, co-firing was
shown to have beneficial synergisms in reducing the emissions of SO2,
NOx, and CO2 of coal [7,11,14,32,37,39–44]. Higher boiler efficiencies
and fuel cost savings have also been reported [7,40,41]. However,
comparative SO2 and NOx emissions from the combustion of coals
blended both with raw biomass and with their torrefied biomass deri-
vatives are hard to find in the literature, thus this investigation was
undertaken to fill this gap.
1.2.3. HCl emissions
Like SO2 and NOx, hydrogen chloride (HCl) not only can contribute
to corrosion inside a boiler, but it can also contribute to acid rain [45].
Fuel-bound chlorine can be released as HCl, Cl2, or alkali chlorides
mainly potassium chloride (KCl), sodium chloride (NaCl), and calcium
chloride (CaCl2) [46–48]. Previous studies [49–51] showed that HCl
and particulate chlorine are the dominant products in the combustion
effluents of biomass. To alleviate boiler deposition and corrosion, pos-
sible solutions include lowering the share of biomass in the fuel blend,
using low chlorine and low alkali content biomass, injecting sorbents
(such as limestone) in the furnace and pre-treating the fuel [52–59]. As
will be shown later in the manuscript, this work demonstrated that co-
firing coal with torrefied biomass is an additional (partial) solution to
the aforementioned boiler issues. Aho and Ferrer [54] reported on the
positive effects of alumino-silicates and sulfur in preventing chlorine
deposition on boiler surfaces by blending coal with high chlorine bio-
mass. Others [56,57] have reported that co-firing low-chlorine biomass
(wood with < 0.01% Cl) with coals (0.09–0.17% Cl) can be favorable in
reducing the HCl emissions from the coals. Alkali chlorides (mostly KCl)
contribute to high-temperature corrosion inside the boilers, and co-
364
Fuel 211 (2018) 363–374
firing high-sulfur fuels with biomass can curtail the amount of KCl
produced [60,61]. It should be mentioned that decreasing the amount
of KCl can increase the concentration of HCl, as it is the product of
chlorine sulfation reactions [60,61].
1.3. Pre-treatment of biomass
Biomass pre-treatments, such as pelletization and torrefaction, in-
crease the energy density and improve transport and storage [62–65].
Torrefaction is a partial thermal decomposition of biomass that leaves a
high-energy dense substance with smaller particle size and much less
moisture [66]. Torrefaction improves the grindability of biomass and
renders it suitable for co-firing with coal, as the torrefied biomass has
similar properties to coal [67–70]. Torrefaction not only reduces SO2
and sometimes NOx emissions, but it also reduces the chlorine content
of biomass [30,71]. For instance, it has been reported that torrefaction
can reduce the chlorine content of biomass by 20–70% [71–76] and the
sulfur content by 30–80% [30]. The release of chlorine inside low
temperature torrefaction reactors is likely to be less problematic than
inside high-temperature boilers. However, to implement torrefaction a
significant investment is required, and to compensate for such invest-
ment large amounts of biomass feedstock need to be processed [1].
Whereas co-firing of coal and raw biomass has been studied ex-
tensively in the past and there have been reports on the gaseous
emissions therefrom, little if any has been reported on the emissions
from co-firing coal with torrefied biomass. This work aims to compare
the gaseous emissions of carbon, sulfur and nitrogen oxides as well as
hydrogen chloride acid gases from co-firing coal with biomass in both
their raw and torrefied states.
2. Experimental procedure
All solid fuels were burned in an electrically-heated, laminar-flow,
alumina drop-tube furnace (DTF), manufactured by ATS. A schematic of
the combustion setup is shown in Fig. 1. A water-cooled injector was
used to introduce particles to the top of a 25 cm long and 3.5 cm in
diameter heated zone section in the furnace. For combustion of streams
of pulverized solid fuels, a bed of particles was placed in a vibrated
glass vial (test-tube), which was advanced by a constant-velocity syr-
inge-pump (Harvard Apparatus). Fuel particles were entrained in me-
tered air, and entered a long capillary tubing (with 1.8 mm inner dia-
meter), procured from McMaster. The tubing was vibrated to its natural
frequency, by two vibrators (12 V 2000 RPM 0.05 A DC Mini Vibration
Motor), to ensure an unimpeded flow of particles to the DTF through a
water-cooled stainless steel furnace injector. Most experiments were
conducted at a constant setting in the syringe pump - driven fuel feeder
of this experimental setup, i.e., by feeding pulverized solid fuel beds at
a constant volumetric flow rate. However, as the bulk bed densities of
pulverized biomass and coal differed drastically, the mass flow rates
also differed accordingly. Hence, additional experiments were per-
formed where the mass feeding rates of the fuels were equalized. To
achieve such analogy, the mass feeding rates of the blends were kept
constant, while those of the coals were decreased mildly and those of
biomass were increased significantly. Since corn straw performed er-
ratically under such higher feeding rates, as it consists of needle-shape
particles [30], results therefrom are not included in this manuscript,
and only those of coals and rice husk, which consists of chunky particles
[30] that fluidize well, are presented herein. Air was introduced to the
hot zone of the DTF through both the particle injector and through a
concentric annular space between the furnace injector and the alumina
drop-tube. The furnace was sealed and the effluent gases and solids
from the combustion of dilute clouds of particles in controlled atmo-
spheres were monitored. Furnace wall temperatures, Twall, were con-
tinuously monitored by type-S thermocouples attached to the wall. The
gas temperature along the centerline of the radiation zone of the fur-
nace was measured to be ∼50 K lower than the tube wall temperature,
E. Rokni et al.
Twall. The full axial gas temperature profile has been given in Fig. 3 of
Ref. [27]. The air flow rate was kept at 2 l/min through the flow
straightener and 2 l/min through the furnace injector. The combined
flow at furnace wall temperatures of 1400 K resulted in an average gas
velocity of 30 cm/s and a nominal gas residence time of about 1s inside
the furnace radiation cavity. The effluent of the furnace passed through
a glass condenser, placed in an ice-bath, and it was then channeled to
the following analyzers: (a) a Teledyne UV-based SO2 analyzer Model
T100H, (b) a Teledyne chemiluminescent NOx analyzer Model T200H,
O2, CO, and CO2 Horiba VIA-510 analyzers as well as a California CO,
and CO2 analyzer. LabVIEW software running on a micro-computer
recorded the analyzer signals through a Data Translation (PCI-6221)
acquisition card. HCl emissions were monitored by Fourier Transform
Infra-Red (FTIR) spectroscopy (using a GASMET DX4000 instrument)
and sampling through a heated line, as described in our prior work
[71]. All experiments were repeated three times and each point shown
on each plot represents the mean of the three tests; the error bars re-
present the standard error of the mean. The schematic includes a se-
lected image from high-speed and high-resolution cinematography in a
drop tube furnace (DTF) of early stage combustion events of free-falling
dilute particle clouds form a 50–50 wt% blend of pulverized bituminous
coal (Illinois #6) with raw corn straw biomass. The bituminous coal
particles formed bright elongated envelope flames of burning volatiles,
topped with long contrails of luminous soot, see Fig. 1. Biomass parti-
cles formed spherical volatile matter flames around individual particles.
Their luminosity was lower than the luminosity of bituminous coal
particles [77]. Inside the volatile matter envelope flames, biomass
particles were seen to rotate, and to consistently shrink. In addition, the
envelope flame luminosity of torrefied biomasses particles was visibly
higher than the flame luminosity of raw biomass particles, which has
been documented in previous research in this laboratory [78,79].
365
Fuel 211 (2018) 363–374
Fig. 1. Schematic of electrically heated DTF for solid fuel
combustion and emission monitoring. The inserted photo-
graph shows particles of 50–50 wt% blend of Illinois coal
(the five particles with contrails in the upper left corner)
and raw corn straw (the remaining five particles) during
their volatile matter combustion phase.
3. Fuel properties
A low sulfur, high alkali sub-bituminous coal (PRB, Wyodak,
Wyoming) and a high sulfur, low alkali bituminous coal (Illinois #6)
were procured from the Penn State Coal Sample Bank, and have been
extensively characterized in prior work [80,81]. Corn straw and rice
husk were obtained from farms at the vicinity of Harbin Institute of
Technology in China and were pulverized by grinding. The Ultimate
and Proximate analysis of all fuel samples are shown in Table 1. The
entire Proximate and Ultimate analyses of the coal samples was per-
formed by the Penn State Coal Sample Bank, whereas the Proximate
and Ultimate analyses of the biomass samples were performed at
Harbin Institute of Technology, based on the GB/T 212-2008 and GB/T
30733-2014 Chinese standards respectively. The sulfur analysis of the
biomass samples was performed based on the GB/T 214-2007 standard
and the heating values were measured according to GB/T 213-2008
standard. The Proximate Analysis numbers add up to 100%, whereas
the Ultimate Analysis numbers do not add up to 100% because not all of
the ash components are listed in Table 1. The coal particles were sieved
and then collected in the range of 75–90 µm and the biomass particles
(both the raw and the torrefied) were sieved and collected in the range
of 90–150 µm. The aspect ratio of the biomass particles can be much
higher than those of coal, particularly those of the corn straw which are
needle-shaped. Hence, while their diameters were in the aforesaid
range their lengths were much higher. The torrefaction process for the
biomass samples was carried out in a laboratory-scale muffle furnace in
a nitrogen flow, as described in Ref. [30]. The data presented in Table 1
show that upon torrefaction the volatile contents of both types of bio-
mass decreased, while the amounts of fixed carbon and ash increased.
In addition, upon torrefaction the mass fraction of nitrogen content
increased by about 20% in both biomass samples while the mass
E. Rokni et al. Fuel 211 (2018) 363–374

Table 1
Chemical compositions (wt%) and energy contents (MJ/kg) of the fuels.

fraction of sulfur decreased by about 60% in both cases. The mass

fraction of alkali contents increased in the case of torrefied biomass as
the concentration of the residual ash in the fuel increased, while the
mass fraction of chlorine content in torrefied biomass decreased by
40–70%. All the fuel samples were dried out inside an oven at 100 °C
overnight prior to the experiments to make sure the moisture contents
of the samples are negligible.

4. Results and discussion

Combustion of pulverized coal and biomass was first conducted at

constant fuel bed volumetric flow rates. However, as the density of
pulverized biomass was lower than that of the coals, additional ex-
periments were also conducted at constant fuel mass flow rates. In all
experiments, neat coals, neat raw and torrefied biomass, as well as
50–50 wt% blends thereof were burned in air, under fuel-lean condi-
tions. In addition in all experiments the bulk (global) equivalence ra- Fig. 2. Bulk (global) equivalence ratios, ϕs, of neat coals, neat biomass, and 50–50 wt%
tios, ϕ, were calculated based on Eq. (1) based on the input of fuel and blends thereof in experiments where the volumetric flow rate of pulverized fuel beds was
kept constant.
air, are shown in Fig. 2.
mf
( m ) actual
air feeder. The lower ϕ of the raw corn straw sample can be partly ex-
ϕ= mf
( m ) stoichiometric plained based on its low bulk density, as its particles are needle-shaped.
air (1)
The bulk bed densities of raw and torrefied corn straw were determined
to be approximately 0.25 g/cm3 and 0.35 g/cm3, respectively; whereas
4.1. Combustion experiments with constant fuel bed volumetric flow rate those of raw and torrefied rice husk were determined to be about
(variable mass flow rates and, thus, variable equivalence ratios) 0.35 g/cm3 and 0.45 g/cm3, respectively [30]. The torrefied biomass
samples experienced higher ϕs in general, as their bulk densities are
In these experiments the volumetric flow rates of the pulverized fuel higher than those of the raw samples. The neat coal samples experi-
beds were kept constant, while the attained bulk equivalence ratios enced the highest ϕs due to their higher bulk densities than those of the
differed due to variant bulk bed densities. In the cases of the two coals ϕ biomass samples. As expected, the equivalence ratios of the 50–50 wt%
was approx. 0.55, whereas in the case of corn straw ϕs were around blends were in-between the values of their corresponding neat coal and
0.13 and 0.20 for its raw and torrefied states, respectively. In the case of biomass components. For those experiments where the mass flow rates
rice husk ϕs were around 0.24 and 0.27 for its raw and torrefied states of the pulverized fuel beds were kept constant, described in a
respectively, at the same settings of the syringe pump – driven fuel

366
E. Rokni et al.
Fig. 3. Combustion efficiencies of neat coals, neat biomass, and 50–50 wt% blends
thereof in experiments where the volumetric flow rate of pulverized fuel beds was kept
constant.
subsequent sub-section, the equivalence ratio was kept at ϕ ≈ 0.4.
4.1.1. Combustion efficiencies
Combustion efficiencies were calculated as shown in Eq. (2), based
on the mass fraction of carbon in a fuel sample introduced to the fur-
nace that was converted into the carbon in the emitted CO2; they are
plotted in Fig. 3. Such efficiencies include any small losses of fuel
powders that may have happened in the feeding tube.
mcarbon in CO2
Combustion Efficiency (%) = × 100
mcarbon in fuel
In all cases, these efficiencies were determined to be between 87%
and 100%. The neat bituminous and sub-bituminous coals experienced
90% and 95% combustion efficiencies, respectively. The torrefied bio-
mass samples experienced higher combustion efficiencies than the raw
samples. Similarly, the 50–50 wt% blends of coal with torrefied bio-
mass experienced higher combustion efficiencies than those of coal
with raw biomass. Discrepancies between the combustion efficiencies of
torrefied and raw biomass can be, at least partially, attributed to the
fact that torrefied biomass is less fibrous than raw biomass and its
particles have lower aspect ratios [79]. Thus, it fluidizes better and,
upon entering the furnace, it may achieve better dispersion and more
effective mixing with air, aiding its burnout. As torrefied biomass is less
fibrous the size distribution of its particles in a given size cut was vi-
sually observed to be more uniform, and long needle-shaped particles,
which are present in raw biomass and are more difficult to burn, are
thus avoided. Torrefied corn straw also contains more carbon than raw
corn straw, which generated more carbon dioxide which, in turn, in-
creased the combustion efficiency, as calculated from Eq. (2). An ad-
ditional observation is that the rice husk biomass and its blends with
coals experienced higher combustion efficiencies than the corn straw
biomass and its blends with coals. The, higher combustion efficiencies
in the case of rice husk and its blends with coal are also attributed to
their lower aspect ratio than those of corn straw [30], which facilitates
their fluidization, dispersion, mixing with air and burning in the fur-
nace.
4.1.2. CO2 emissions in the combustion effluents
The measured volume fractions of CO2 in the combustion effluents
of all samples are shown in Fig. 4 (a- representing bituminous coal-
biomass samples, and b- sub-bituminous coal-biomass samples). The
mole fractions of CO2 in the neat coal effluents were about 9%, as also
reported in the previous works under similar conditions [80,81]. For all
neat raw and torrefied biomass samples the mole fractions of CO2 were
between 2.2% and 5.5%, of which the lowest number corresponds to
Fuel 211 (2018) 363–374
corn straw and the highest to rice husk samples, for the reasons men-
tioned before. In addition, the torrefied corn straw generated higher
CO2 emissions in line with its higher carbon content. For the 50–50 wt
% blends of coal and biomass the CO2 emissions were between 4.3%
and 7%; rice husk (raw and torrefied) blends generated higher emis-
sions than corn straw (raw and torrified) blends. Moreover, torrefied
biomass in the 50–50 wt% blends generated higher CO2 emissions than
raw biomass. These disparities can be attributed to the differences in
the bulk equivalence ratios ϕ among the fuel samples and to differences
in their carbon contents. Emission yields (mass based emissions), i.e. g/
(g dry fuel), were also calculated to normalize such discrepancies in the
CO2 mole fractions. As shown in Fig. 4, the emission yields of neat corn
straw(raw) and rice husk(raw) were around 1.5 and 1.6 g/(g dry fuel),
which are lower than the 2.11 and 2.43 g/(g dry fuel) for bituminous
and sub-bituminous coals respectively. Emission yields from combus-
tion of the blends were between 1.8 and 2.15 g/(g dry fuel); those from
corn straw – coal blends were slightly higher than those of rice husk
blends. Subsequently, the CO2 emission yields were further normalized
with the energy contents of the fuels listed in Table 1, i.e., kg/(GJ of
fuel burned), and such emission factors are also shown in Fig. 4. As the
energy contents of neat coals are higher than those of the 50–50 w%
blends, and those of the blends are higher than those of the neat bio-
mass, then in general the emission factors are inversely proportional to
the fuel energy contents. The CO2 emission factors range from 75 to
108 kg/GJ. It is notable that all biomass samples have higher CO2
emission factors than those of coals burned herein because of their
lower heating values. In agreement with the aforesaid observations, the
O2 mole fractions in the effluents were inversely proportional to the
emitted CO2, as shown in Fig. 4.
(2) 4.1.3. SO2 emissions in the combustion effluents
The measured mole (volume) fractions of SO2 in the combustion
effluents of all samples are shown in Fig. 5, together with the mass
emission yields, the emission factors and the mass fractions of sulfur
converted to SO2. The SO2 emissions from the bituminous coal were the
highest at 3180 ppm or 110 mg/g of dry coal, see also [80], followed by
sub-bituminous coal at 188 ppm or 7.2 mg/g of dry coal. The SO2
emissions from burning biomass were much lower. The SO2 emissions
of corn straw, raw and torrefied, were 17 and 9 ppm respectively,
which correspond the mass emissions of 1.7 and 0.75 mg/g of dry fuel
and to emission factors of 0.1 and 0.04 kg/GJ respectively. The SO2
emissions for the rice husk, raw and torrefied, were 10 and 5 ppm re-
spectively, which correspond to mass emission yields of 0.5 and
0.24 mg/g of dry fuel, and to emission factors of 0.035 and 0.015 kg/GJ
respectively. It was calculated that the coal samples emitted most of
their sulfur as SO2, amounting to 83% and 100% for sub-bituminous
and bituminous respectively. The biomass samples emitted much lower
fractions of their sulfur content as SO2, ranging between 20% and 43%
in all cases, including raw and torrefied, and was mainly attributed to
higher sulfur retention in their alkali-rich ashes.
For the all cases of the 50–50 wt% blends the SO2 mole fractions,
mass emission yields, and emission factors were in-between those of
neat coals and neat biomass. The fact that such values are much lower
than those of coal constitutes a significant benefit of co-firing coal and
biomass. In addition to replacing high sulfur coal with low sulfur bio-
mass, a beneficial synergism is also evident which reduces the SO2
emissions to even lower values than those predicted based on linear
interpolations between the values of neat coal and biomass. This can be
attributed to the high alkali earth metal content of biomass that can
capture gas-phase SO2 heterogeneously in the ash. Capturing sulfur by
alkali metals available in the fuel structures was extensively studied in
previous research in this laboratory [80–83]. To support this argument
herein, sufficient amounts of ash were generated and analyzed for their
sulfur contents, as described in Section 5. Upon further examination of
Fig. 5, it becomes evident that the SO2 emissions from burning torrefied
biomass were lower than those from raw biomass, as also shown in
367
E. Rokni et al. Fuel 211 (2018) 363–374

Fig. 4. Carbon dioxide mole fractions (%), mass fractions based on the amount of fuel introduced to the furnace (g/g), and corresponding emission factors (kg/GJ), followed by mole
fraction of oxygen(%) in combustion effluents. (a- represents bituminous coal – biomass samples, and b- represents sub-bituminous coal – biomass samples). In these experiments the
volumetric flow rates of pulverized fuel beds were kept constant.

Fig. 5. Mole fractions of sulfur dioxide in the combustion effluents (ppm), mass fractions based on the amount of fuel burnt inside the furnace (mg/g), corresponding emission factors (kg/
GJ) and conversion amounts of the fuel sulfur to SO2, (a- represents bituminous coal – biomass samples, and b- represents sub-bituminous coal – biomass samples). In these experiments
the volumetric flow rates of pulverized fuel beds were kept constant.

368
E. Rokni et al.
previous work [30] and reflects the lower sulfur content of the torrefied
biomass, as shown in Table 1. During the process of torrefaction (low-
temperature pyrolysis) sulfur was released to the gas phase, as also
documented in other studies where torrefaction at different tempera-
tures resulted in reduction of the sulfur contents of different types of
biomass [76,84]. Sulfur can be found in both organic and inorganic
compounds in biomass. The organic sulfur can be released during bio-
mass devolatilization at low temperatures (akin to the torrefaction
temperatures used in this work). The inorganic sulfur can be released at
high temperatures (above 900 °C) through interaction with the char
matrix; or it can be retained in the ash [76]. A significant release of
sulfur from six different biomass types has been reported to be up to
60%, when torrefaction occurred at 350 °C [76], whereas for herbac-
eous biomass it has been reported to be 35–50% when pyrolysis oc-
curred at 400 °C [76,85,86]. Thus, in this study organic-bound sulfur
must have been released during the torrefaction, which lowered the
sulfur content of torrefied biomass, as shown in Table 1. Hence, it can
be concluded that torrefaction reduced the amount of SO2 emissions in
the effluent gases and, consequentially, torrefied biomass generated less
SO2. Finally, by comparing the rice husk and corn straw biomass herein,
the former samples contain less sulfur, therefore their mass emission
yields and their emission factors were lower as expected. In addition,
the emissions from blends of coals with torrefied biomass were lower
than those of coal with raw biomass due to lower sulfur content of the
coal-torrefied biomass blends.
4.1.4. NOx emissions in the combustion effluents
Experimental results in Fig. 6 show the NOx emissions in the com-
bustion effluents of the fuels, as mole fractions, as mass-based emission
yields, as emission factors, and as percentages of fuel-nitrogen con-
verted to NOx, respectively. Generally, the nitrogen content of coals
varies less [87] than that of different types of biomass. The nitrogen
Fig. 6. Mole fractions of nitrogen oxide in the combustion effluents (ppm), mass fractions based on the amount of fuel burnt inside the furnace (mg/g), corresponding emission factors
(kg/GJ) and conversion amounts of the fuel sulfur to NOx, (a- represents bituminous coal – biomass samples, and b- represents sub-bituminous coal – biomass samples). In these
experiments the volumetric flow rates of pulverized fuel beds were kept constant.
369
Fuel 211 (2018) 363–374
content of the fuels herein is in the range of 0.94–1.5 wt%, and all
biomass samples have higher nitrogen contents than the coals, see
Table 1. Monitored mole fractions (ppm) of NOx in the biomass ef-
fluents were lower than in those of the coals, see Fig. 6, because of the
lower bulk equivalence ratios in these experiments, therefore, to allow
direct comparison, mass emission yields were calculated based on the
mass of fuel burnt (specific mass emissions) and then, again, emission
factors were obtained based on the energy content of the fuels. The
emissions from burning bituminous and sub-bituminous coals were 690
and 575 ppm respectively, which correspond to 11.2 and 10.3 mg/g of
dry fuel, and 0.4 and 0.35 kg/GJ, respectively. NOx emissions from raw
and torrefied rice husk were 185 and 230 ppm, respectively, which
represent 3.2 and 3.6 mg/g of dry fuel, respectively, and 0.22 kg/GJ in
both cases. Finally, NOx emissions from raw and torrefied corn straw
were 144 and 288 ppm, respectively, resulting in 4.8 and 6.1 mg/g of
dry fuel, and 0.29 and 0.32 kg/GJ respectively. The fact that corn straw
generated higher specific emissions of NOx than rice husk may be at-
tributed to its higher nitrogen content and to its higher volatile content,
which facilitates release of fuel-bound nitrogen. The torrefaction pro-
cess increased the mass fraction of nitrogen content of fuels, as shown
in Table 1, therefore NOx emission yields from torrefied biomass were
typically higher than those from raw biomass. Under the strongly fuel-
lean conditions of this work, less than 40% of the fuel-nitrogen of the
coals was converted to NOx, as it was also reported in previous research
[27,88]. It is notable, that even if the biomass samples contained more
nitrogen than coal, they emitted less NOx, which indicates different
conversion pathways for the fuel-N (e.g., the heightened importance of
the NH3 route in comparison to the HCN route, etc. [27–29,32]). In fact,
in the cases of raw and torrefied rice husk the amount of fuel-nitrogen
converted to NOx was less than 13%, while for the raw and torrefied
corn straw raw the corresponding fractions of fuel-nitrogen converted
to NOx were about 19% and 28%, respectively. Generally, as some raw
E. Rokni et al.
corn straw particles may have a delayed and prolonged combustion due
to their typically bigger particle masses and, if not fully dried, higher
moisture content compared to coal, a lower fraction of their volatile
nitrogen components may be converted into NO, due to encountering
lower local oxygen concentrations [28,29]. The NOx emissions of all
blends were between those of the corresponding neat coal and neat raw
or torrefied biomass. In the case of coal-torrefied biomass co-firing, the
mass emissions and emission factors were lower than those predicted by
a linear interpolation of the emissions of the neat fuels, which is a result
of possible different release mechanisms and/or the presence of bene-
ficial NOx reduction synergisms during the combustion of these blends.
For instance, as biomass has a high volatile content, it may serve as a de
facto re-burn fuel for NOx reduction from the coal combustion, which
gives a further potential to decrease the NOx emissions from the blend
[14]. There may also be a temperature contribution to the fact that the
NOx emissions from the blends of coal with torrefied biomass were
lower than predicted, as ongoing research by the authors shows that
torrefied biomass chars burn cooler than coal chars. Other researchers
have also reported the positive influence of higher volatile content on
NOx until the fuel volatility (defined as volatile matter/fixed carbon)
reaches unity [38]. It has been also reported that the NOx emissions
from combustion of raw and torrefied biomass decrease with the in-
crease in volatility [30], which was also seen in the experiments of this
work, as the raw biomass samples contain more volatile matter than the
torrefied samples. In addition, it was reported that the NOx emissions
decrease with the increase of calcium and magnesium over nitrogen,
since the CaO and MgO in fuel structure can form active sites that
would catalyze the reduction of NO [89,90].
4.1.5. HCl emissions in the combustion effluents
The specific mass-based emissions of HCl from the combustion of
both coals (Illinois and PRB), corn straw (raw and torrefied), and
50–50 wt% blends of either coal with corn straw are shown in Fig. 7.
The HCl emissions from corn straw were found to be much higher than
those from either of the two coals, which is expected based on the much
higher Cl content of corn straw than those of the coals (see Table 1).
It is notable, however, that the HCl emissions from the 50–50 wt%
blends of either of the two coals with the raw corn straw were higher
(by about 39% and 22% for I-CS(R) and PRB-CS(R) samples,
Fig. 7. Mass fraction of hydrogen chlorides (mg/g of fuel burned) in combustion effluents
of Illinois (I), PRB, raw corn straw (CS(R)), torrefied corn straw (CS(T)), and their blends.
370
Fuel 211 (2018) 363–374
respectively) than the predicted values from linear interpolations of the
corresponding emissions of their constituents. The amounts of such
additional HCl that appeared during combustion of the blends may be
partly attributed to homogeneous reactions of alkali chlorides (mostly
KCl) with SO2 gases released from the combustion of the coals, as ex-
plained in the ensuing paragraph. This hypothesis is supported by the
fact that more HCl was found in the gas phase when corn straw was co-
fired with the high-sulfur Illinois coal than with the low-sulfur PRB
coal. In the case of burning 50–50 wt% blends of both coals with the
torrefied corn straw the HCl emissions were also higher than values
expected from a linear interpolation of the corresponding emissions
from burning their constituents, but by a lesser amount than in the case
of coal blends with the raw corn straw (by about 5% and 9% for I-CS(T)
and PRB-CS(T) samples, respectively). This may be explained based on
the much lower chlorine content of the torrefied biomass – coal blends,
as compared to the raw biomass – coal blends by factors of nearly 3.
Sulfation reactions of alkali chlorides are important, as they have
been reported to lessen the severity of corrosion and fouling problems
inside the boilers [91]. Such a reaction with KCl is exemplified below:
1
2KCl (g,c) + SO2 + O2 + H2 O(g) ⇆ K2SO4(g,c) + 2HCl (g)
2 (3)
The thermodynamic chemical equilibrium constant, Kp, can be
calculated based on the Gibbs Free Energy (G) change as follows:
−ΔGTo
ln Kp =
RT (4)
where Gibbs free energy ΔGTo is defined as follows:
ΔGTo = ΔHTo−T ΔSTo (5)
where ΔHTo is the standard enthalpy change, ΔSTo
is standard molar
entropy change, and T is the reaction temperature. The calculated Kp
for Eq. (3) for KCl (in gaseous state) and KCl (in condensed state) are
shown in Eqs. (6) and (7), respectively:
28880 −1
Kp = 9.58 × 10−5e T atm 2 (6)
78700 −5
Kp = 1.045 × 10−12e T atm 2 (7)
Eqs. (6) and (7) are shown in Fig. 9(a), plotted versus reaction
temperature. Whereas increasing temperature is not favorable for the
sulfation of KCl, at the furnace gas temperature attained in this work,
Tgas = 1350 K, the gas-phase reaction is more than likely to take place.
In addition, published results by Lisa et al. [91] suggest that most of the
KCl sulfation in a boiler can be expected to occur in gas phase. Their
experiments [91] took place inside a laminar entrained-flow reactor
operated at temperatures in the range of 1150–1350 K and residence
times in the range of 0.24–1.22 s, both which are pertinent to the ex-
perimental conditions found herein. For the chemical reaction of Eq.
(3), higher SO2 concentrations can increase the HCl emissions in the
flue gases, as observed in the experimental results herein (Fig. 7). A
prior investigation [91] reported that the sulfation rates in both molten
and gas phases depend on the concentrations of SO2, and O2, but not
H2O, based on experiments in an entrained flow reactor; and showed
that SO3 is also available for sulfation of alkali chlorides. Yet, another
investigation reported that homogeneous formation of SO3 from SO2
amounted to 1.8% of 1000 ppmv SO2 introduced in a flow reactor,
heated to 1400 K [92]. In agreement with that work, for the case of the
high-sulfur Illinois bituminous coal burned herein, previous experi-
ments by the authors detected about 68 ppm of SO3 (corresponding to
2% of total sulfur of the coal) in the flue gases [81].
4.2. Combustion experiments with constant mass flow rate and, thus,
constant bulk (global) equivalence ratio
The results in the previous sections were obtained with nominally
constant volumetric flowrate of the fuel powders in the furnace. This
E. Rokni et al.
Fig. 9. Equilibrium constants for KCl (condensed or gas) sulfation reactions versus tem-
perature.
caused notable differences in the mass flowrate and the resulting
equivalence ratios, as seen in Fig. 2, depending on the bulk densities of
the powders. Hence, a limited number of additional experiments were
performed with comparable mass flow rates of the pulverized fuels to
investigate the validity of the conclusions. The equivalence ratios in
these experiments were kept constant at approx. ϕ = 0.4. The corn
straw was not included in these experiments as some fluidization dif-
ficulty was encountered in maintaining the higher mass flow rate
needed to attain ϕ = 0.4. To the contrary, rice husk fluidized equally
well as the coals. Mass-based emissions of CO2, SO2 and NOx from the
combustion of the bituminous coal (Illinois), raw and torrefied biomass
(rice husk), and their 50–50 wt% blends are shown in Fig. 8. Therein,
results obtained with constant powder volumetric flowrate, shown be-
fore, are also superimposed for comparison. The specific mass-based
emissions of CO2 and SO2 were fairly similar in both types of experi-
ments (constant mass flowrate and constant volumetric flowrate of the
powders). However, the NOx emissions for the raw and torrefied rice
husk samples almost doubled in the constant mass flow rate experiment
which was conducted at a higher equivalence ratio, which itself almost
doubled (from ϕ = 0.2 in the constant volumetric flowrate to ϕ = 0.4)
in the constant mass flowrate experiments. It is likely, but it was not
documented, that at the higher ϕ the mass flow rate fluidization of the
pulverized biomass was steadier, resulting in better combustion and
more NOx.
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Fuel 211 (2018) 363–374
Fig. 8. Mass fractions of CO2, SO2, and NOx based on the
amount of fuel burnt inside the furnace (g/g & mg/g). All
experiments have similar equivalence ratios (ϕ = 0.4). In
these experiments the volumetric flow rates of pulverized
fuel beds were kept constant.
5. Ash analysis
Additional experiments to assess the chemical composition of the
ashes and investigate the validity of the aforesaid explanations on the
fate of the gaseous pollutants were performed by burning fixed-beds of
fuel in a horizontal muffle furnace. This was done to collect sufficient
amounts of ashes for reliable elemental analysis, which was performed
by Ion Chromatography (IC). That furnace was operated under atmo-
spheric conditions and combustion occurred in air. The furnace was
preheated to 1400 K and a porcelain boat containing a known quantity
of fuel was expediently inserted. Thereafter the fuel experienced a
heating rate of 103 K/s. Upon combustion, the ashes were cooled and
collected for analysis. Prior to characterization, the ashes were dried at
105 °C for 2 h. Then, they were placed into an ultra-high purity (metal
impurity content is less than 1 ppb) solution (HNO3: 6 ml, H2O2: 2 ml)
for two hours. Afterwards, a new solution (HNO3:H2O2:HF = 4:2:2)
was added and the samples were heated to 120 °C at a heating rate of
20 °C /min and were kept at the maximum temperature for 5 min.
Subsequently, the samples were heated to 200 °C with a rate of 16 °C
/min and kept at that final temperature for one hour. Thereafter, the
solutions were detected by IC with a Dionex ICS-900 instrument. The
abbreviations used in Table 2 are for the following samples: corn straw
raw (CS(R)), corn straw torrefied (CS(T)), rice hush raw (RH(R)), rice
husk torrefied (RH(T)), Illinois coal (I), Powder River Basin coal (PRB).
The results shown in Table 2 include the total alkali in the neat
biomass fuels and their blends with coal, as well as the percentages of
nitrogen, sulfur, and chlorine detected in the ashes of each sample upon
combustion. Based on the amounts of these elements contained in the
fuels and those contained in their combustion ashes, the fractions of the
elements that were captured in the ashes were calculated. Then by di-
viding these fractions of N, S, and Cl captured in the ashes by the total
initial alkali mass in each fuel sample, the retention effectiveness of the
alkalis for these elements was assessed, and listed in Table 2. (i) For
sulfur, such ratios are higher in the cases of blends of the biomass with
the high-sulfur Illinois coal, as the biomass fuels have high alkali con-
tents and this coal emits copious amounts SO2. Similar results were seen
in prior work when this high-sulfur coal was blended with a low-sulfur-
high alkali lignite [80,81]. (ii) For chlorine, such ratio is the highest for
raw corn straw and for its blends with the Illinois coal, as raw corn
straw has high chlorine and high alkali contents. (iii) For nitrogen these
ratios vary in a much narrower range than those for sulfur and chlorine,
as all fuels contain similar amounts of nitrogen. Overall, the amounts of
nitrogen captured in the ashes of the torrefied biomass samples and in
their blends with coal were higher than the nitrogen captured in the
ashes of the raw biomass samples and their blends with coal. This can
be attributed to the higher amounts of ash, especially alkali metals, in
the torrefied samples, as shown in Table 1. It has been reported that ash
elements can inhibit the conversion of fuel-N to NO [93]. It has also
been reported that Mg, Ca, and K can contribute to catalytic activity in
E. Rokni et al.
Table 2
Percentage of fuel-N, S, and Cl converted to NOx, SO2, and HCl as well as the amount of these elements retained the ash.
NO reduction from char combustion [93–96]. The NO reduction by the
alkali metals could may partially explain the observed lower NOx
emissions, shown in Fig. 6, from burning blends of coal with torrefied
biomass which have higher concentrations of alkali metal elements
than their raw biomass precursors.
6. Conclusions
This research burned blends of two coals, a high-sulfur bituminous
coal (Illinois #6) and a low-sulfur sub-bituminous coal (PRB), with two
types of biomass, a herbaceous (corn straw) and a crop related (rice
husk). The acid gas emissions (SO2, NOx, and HCl) of the neat coal,
biomass, and their 50–50 wt% blend were monitored. The following
quantitative observations were made:
• Specific CO 2 mass emissions (normalized by fuel mass) from co-
firing coals with torrefied biomass samples were typically higher
than those from co-firing coals with raw biomass samples. These
discrepancies can be attributed to the differences in their carbon
contents of raw and torrefied biomass.
• Specific SO2 mass emissions (normalized by fuel mass) from co-
firing a high-sulfur bituminous coal with raw and torrefied corn
straw were reduced by 35% and 46%, respectively, from the ex-
pected values of a linear interpolation of the corresponding emis-
sions of their constituents. Corresponding SO2 reductions from co-
firing this coal with raw and torrefied rice husk were 37% and 50%,
respectively.
• Specific SO2 mass emissions (normalized by fuel mass) from co-
firing a low-sulfur sub-bituminous coal with raw and torrefied corn
straw were reduced by 26% and 33%, respectively, from the ex-
pected values of a linear interpolation of the corresponding emis-
sions of their constituents. Corresponding SO2 reductions from co-
firing this coal with raw and torrefied rice husk were 19% and 36%,
respectively.
• Specific NOx mass emissions (normalized by fuel mass) from co-
firing a high-sulfur bituminous coal with raw and torrefied corn
straw were reduced by 6% and 17%, respectively, from the expected
values of a linear interpolation of the corresponding emissions of
their constituents. Corresponding NOx reductions from co-firing this
coal with raw and torrefied rice husk were 10% and 19%, respec-
tively.
•
Specific NOx mass emissions (normalized by fuel mass) from co-
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Fuel 211 (2018) 363–374
firing a low-sulfur sub-bituminous coal with raw and torrefied corn
straw were reduced by 5% and 15%, respectively, from the expected
values of a linear interpolation of the corresponding emissions of
their constituents. Corresponding NOx reductions from co-firing this
coal with raw and torrefied rice husk were 9% and 27%, respec-
tively.
• Specific HCl mass emissions (normalized by fuel mass) from co-
firing a high-sulfur bituminous coal with raw and torrefied corn
straw increased by 39% and 5%, respectively, from the expected
values of a linear interpolation of the corresponding emissions of
their constituents.
• Specific HCl mass emissions (normalized by fuel mass) from co-
firing a low-sulfur sub-bituminous coal with raw and torrefied corn
straw increased by 22% and 9%, respectively, from the expected
values of a linear interpolation of the corresponding emissions of
their constituents.
Acknowledgement
This work has been partially supported by Northeastern University
and partly by the Innovative Research Groups of the National Natural
Science Foundation of China (Grant No. 51421063). Mr. Xiaohan Ren
was supported by the China Scholarship Council.
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