Fuel 253 (2019) 1018–1033

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Fuel
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Full Length Article

Combustion improvements of upgraded biomass by washing and T

torrefaction
Pedro Abelha , Carlos Mourão Vilela, Pavlina Nanou, Michiel Carbo, Arno Janssen, Simon Leiser
⁎

The Netherlands Organization for Applied Scientific Research TNO (ECN part of TNO), P.O. Box 15, 1755 ZG Petten, The Netherlands

ARTICLE INFO ABSTRACT

Keywords: Different streams of low-grade biomass of different origins (road side grass, miscanthus, wheat straw and spruce
Grass bark) were upgraded to reasonable quality commodity fuels by significantly reducing the alkali and chlorine
Straw content, through washing with water in a first step and torrefaction in a second. The aim was to produce a
Pretreatment cleaner fuel with a higher energy content for further densification. The final goal was to demonstrate the im-
Washing
provements attained by the upgrading process during combustion using the lab-scale combustion simulator
Torrefaction
facility of ECN part of TNO.
Alkali
Slagging Analyses of the original, washed and washed/torrefied samples showed that approximately 90% of Cl and up
Fouling to 60–80% of K can be removed by this upgrading route; during the torrefaction step Cl and S are removed from
the solids; during torrefaction K and Na are not significantly altered; the pre-wash step is crucial for the removal
of K. Si and Ca remain largely in the solid fraction; post-wash seems to be a viable route to upgrade dry-type of
biomasses; “straw” like material requires more time for washing than “grass” type.
The combustion results showed that: NOx emissions are generally decreased after upgrading; High tem-
perature chlorine corrosion can be effectively mitigated; Fine particulate matter (submicron/aerosols) formation
is strongly reduced, effectively reducing the risk of alkali induced fouling. However, slagging tests revealed that
pre-washing and torrefaction has minor impact on the slagging propensity of the fuel. Only, slightly reduced
slagging is observable and therefore the use of mineral combustion additives, or smart blending with other fuels
in order to further mitigate the slagging risks is strongly recommended.

1. Introduction
Biomass use is regarded as one of the most important renewable
energy sources for power and heat generation and chemicals. For the
coming decades, it is foreseen that biomass will play a major role to the
circular economy and in the transition to a sustainable society [1,2].
In order to avoid ash related problems in the combustion equipment
like slagging, fouling, corrosion and ash disposal, high quality biomass
fuels are preferred. However, high quality biomass is not available in
sufficient quantities to replace coal, or is available at significant higher
prices than coal.
The increase in biomass demand in the energy sector will stimulate
the interest for alternative low-grade materials such as residues from
agriculture, landscape management and the food industry. At the same
time the use of these low-grade materials will promote new employ-
ment opportunities locally in rural areas and, therefore, also contributes
to the social aspect of sustainability [3,4].
In order to overcome some of the limitations of biomass fuels use,
torrefaction has been presented as a valid route for biomass upgrading.
There are some review works available in literature covering several
types of torrefaction processes from dry inert torrefaction to oxidative
torrefaction, hydrothermal carbonization (HTC) and steam explosion
[5–8], which provides alternative approaches to upgrade solid biomass
materials. HTC is not a mature technique yet. The HTC process is dif-
ficult to operate in a continuous regime, since feeding biomass against
high pressures in a continuous process poses engineering problems [9].
Moreover, the liquid phase can promote corrosion and fouling in the
reactor and piping walls when more severe conditions are used. Fur-
thermore, the effluent water can be difficult to treat by digestion due to
high total organic content (TOC) and toxicity [10–12]. For example
Kambo et al. [12] have found up to 25–30 g/l of TOC in the HTC pro-
cess water (PW) of miscanthus, which increased to over 60 g/l when PW
was recirculated to the HTC process. However, ECN part of TNO has
developed a process (TORWASH®), which is also a wet torrefaction
process making use of milder conditions than HTC, which is well suited
to treat high moisture content biomasses and sludges [13]. This process

⁎
Corresponding author.
E-mail address: pedro.abelha@tno.nl (P. Abelha).

https://doi.org/10.1016/j.fuel.2019.05.050
Received 27 September 2018; Received in revised form 19 April 2019; Accepted 9 May 2019
Available online 23 May 2019
0016-2361/ © 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
P. Abelha, et al.
can be easier applied than HTC, as an alternative to dry torrefac-
tion + washing. Nevertheless, for dry type biomasses, dry torrefaction
followed by washing is preferable.
Dry inert torrefaction combined with densification is a simpler
process, which turns the biomass into a commodity fuel with enhanced
homogeneity, energy density, hydrophobicity and grindability, which
can be handled in a similar way as coal and is suitable to directly re-
place it [14,15]. However, dry torrefaction has severe limitations in
removing alkalis present in the biomass. The major limitation for the
use of low-grade biomass in combustion systems is the higher main-
tenance costs derived from the more frequent and severe sintering,
slagging, fouling and corrosion risks, which are mainly related to the
presence of alkalis and chlorine in the biomass [16]. A recent literature
review covers the issues on ash formation and deposition in coal and
biomass fired combustion systems [17].
Options for reducing the effects of the alkali content in biomass
includes addition of additives [18], blending high-alkali biomass with
materials with higher aluminosilicate and Sulphur content to increase
ash-fusion temperature in the mix [19], or simply reducing of the alkali
content through washing techniques [20–25]
Previous lab and pilot scale studies with grass, straw, bark and
miscanthus showed that about 90%(wt) of the chlorine and between 50
and 80% (wt) of the potassium can be removed by simple tap water
washing at 50 °C [26,27]. Carrillo et al. [23], have found that soaking
sorghum biomass in tap water at 20 °C had a similar effect on total
halogen reduction as double washing (up to 73%), while for K a re-
duction of 62% was achieved. Deng et al. [22] work showed higher
extraction values during washing with demi-water, for both K, up to
90% depending of the biomass material, and Cl up to 95% in the case of
rice straw, most probably due to the higher temperatures of the water
(up to 90 °C), the smaller particle size used (280–450 μm) and to the use
of demi-water. Yu et al. [21] made similar observations during their
washing tests of milled (< 2 mm) biomasses with distilled deionized
water at 22 °C, extracting about 66% of K and 72% of Cl from wheat
straw and about 99% of K, and 85% of Cl from rice straw. Due to this
high levels of alkali and Cl extraction the slagging, fouling and corro-
sion risks are expected to be significantly reduced during combustion
[24,25].
The combination of washing and torrefaction techniques seems to
be an interesting route to upgrade low quality biomass materials for
energy applications. Some work available in literature [26,27] showed
that significant improvements on the fuel quality were attained and
provided experimental data relevant to perform technoeconomic ana-
lysis and upscale the process further to industrial level. However, the
expected combustion improvements were evaluated so far mostly by
fuel characterization results and calculated fuel indexes, usually used
for evaluating emissions, high temperature corrosion and ash melting
tendency, as a first indication of the enhanced performance of the up-
graded biomass fuels [20–23]. There is some combustion experimental
work showing that traditional fuel index calculations, based on coal
combustion experience, are not reliable when applied to biomass
combustion and extensive work has been carried out to find more re-
liable indexes for biomass materials [24–31]. Although these new in-
dexes showed better performance for predicting biomass combustion
behavior than the ones traditionally used for coal, these studies still
point out the limited applicability. Moreover, most part of the experi-
mental tests done to corroborate the applicability of the calculated in-
dexes are based on TGA, or other discontinuous processes, or ash fu-
sibility tests, subjected to low heating rates, which are useful to identify
some mechanisms and interactions with additives, but are far away
from the real conditions experienced in a pulverized fuel system.
The combustion work carried out and described in the current paper
further confirms the fuel quality improvements achieved through up-
grading (washing and dry torrefaction) during live combustion tests,
representing realistic conditions experienced in industrial PF furnaces,
decreasing the uncertainty related to the fuel indexes results. To the
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Fuel 253 (2019) 1018–1033
author’s best knowledge, this is the first time that different low-grade
biomass streams are upgraded by upscaling from lab-scale studies to
pilot scale, integrating both washing and torrefaction, and tested under
representative conditions of PF combustion systems.
2. Material and methods
2.1. Biomass materials
Four low-grade biomasses – road side grass, miscanthus, wheat
straw and spruce bark were used in this study. The biomass materials
were chosen based on their availability and potential energy applica-
tion. They all originated from The Netherlands, except spruce bark,
which originated from Finland.
Road side grass is defined as clippings coming from strips of land
adjacent to road infrastructure. Road-side grass is available in sig-
nificant quantities. About 240,000 ton/year are available on dry basis
only in The Netherlands [32]. Collection routes are already in place for
the road-side grass on a regional level and for this reason there is a
significant potential for its use for energy applications in the country.
The road side grass was received with a moisture content of about 74%
wt and was used directly for washing, as received.
Straw is available in significant quantities and it is a serious problem
in specific parts of the world, for instance where sugar cane and rice are
produced, leaving significant quantities of useless straw behind, which
can no longer be burnt at the field and urgently need alternative routes
to be valorized. Wheat straw originated from the province of North-
Holland, was chosen since it was easy to obtain and served as an ex-
ample of these kind of materials, being an agriculture waste. The straw
was received in 25 kg bales, with a moisture content of 15% wt and was
used directly for pre-washing or torrefaction as received.
Miscanthus can be regarded as an energy crop. At the moment about
25% of the total produced miscanthus from the Netherlands is available
for energy purposes. However, it can be produced in significant quan-
tities in the future if there is a demand. The miscanthus was received
with a moisture content of 14% wt and was used directly for pre-
washing and torrefaction as received.
Spruce bark was chosen based on the excess availability of forest
residues that can be used for energy purposes. The bark used in this
study came from a paper pulp company from Finland, where significant
quantities are being generated and are available for commercial ap-
plication. The bark was received in the form of chips, with a moisture
content of 12% wt and was used directly for pre-washing and torre-
faction as received.
2.2. Biomass upgrading
In order to produce representative quantities of upgraded bio-
masses, a pilot scale washing installation was built. This installation
was assembled inside a container and consists of two washing bins in
sequence working in countercurrent with the water flow to increase the
washing efficiency (removal of Cl and K). The option of using a third
bin was evaluated but it was concluded that the marginal efficiency
gain wouldn’t compensate the extra CAPEX. Tap water, with a con-
ductivity of 500 µS cm−1, was used at a temperature of 50 °C in the first
bin. The feedstock was washed with a moisture content on an as re-
ceived basis and was continuously fed into the first washing bin, with a
minimum residence time of 15 min and then conveyed to the second
washing bin (also at 50 °C) for another minimum 15 min of washing
time. The water temperature was chosen after lab scale optimization
tests [26,27] and the contact time was defined accordingly to the per-
formance of the individual biomasses. Mixing conditions were opti-
mized by the use of paddles that immersed the feedstock and controlled
underwater air jets, which were minimized to prevent excess foaming.
The material was then conveyed out of the second washing bin, rinsed
with fresh water, pressed and finally dried to a moisture content below
P. Abelha, et al. Fuel 253 (2019) 1018–1033

15% (wt). A more detailed description of the washing process is given charring process is intensified [34]. Furthermore, particle size [35] and
in [26,27]. secondary reactions between volatiles and solids [36], which was the
After washing, mechanical dewatering and thermal drying, three of case in this work, also plays a role.
the feedstocks – miscanthus, straw and road-side grass – were pelletized The residence time in the reactor, was around 1 h. A more complete
in order to increase their bulk density and therewith to overcome description of the installation can be found elsewhere [37]. For up-
possible feeding and handling issues in the torrefaction pilot reactor, grading the biomasses at pilot scale, all the materials were first washed
which operates in a moving bed mode and was dimensioned to work and then torrefied, i.e., only pre-washing was done, although washing
with wood chips. Washed miscanthus, straw and road-side grass were after torrefaction was found to be more energy efficient and less ex-
first milled using a hammer mill with a 1.5 mm screen and then pel- pensive for dry type biomasses [38].
letized with a 6 × 30 mm die. The bark didn’t need to be pelletized and
was fed as chips with a maximum size of 100 mm. The three pelletized
2.3. Combustion facility
feedstocks and the bark were torrefied at a feed rate of approximately
50 kg/h. The torrefaction pilot plant consists of three main sections: the
After the upgrading process, the fuels were milled with a variable
feeding and drying section, the torrefaction section and the torrefied
high speed rotor mill using a 1.0 mm sieve to obtain a particle size
product collection section. The biomass is heated up to 150–200 °C in
suitable for testing the Lab-Scale Combustion and Gasification
the drying section and subsequently enters the torrefaction section of
Simulator (LCS). The LCS (Fig. 1) consists basically of a drop tube re-
the pilot plant reactor. The feedstock is heated directly by a recycled
actor with an integrated, premixed and multi-stage flat flame gas
torrefaction gas stream at a temperature of 250–340 °C so that the
burner. The staged gas burner enables high initial particle heating rates
torrefied biomass can reach a temperature of 240–320 °C at the bottom
and temperatures and provides the possibility to simulate air staging as
of the reactor. The torrefaction gas produced in excess is burnt in a
in low-NOX burners and also the presence of specific combustion pro-
combustor and the flue gas is vented to the stack. The torrefied material
ducts such as, e.g., SO2. The facility is also very well suited for oxy-fuel
is extracted at the bottom of the reactor and is transported and stored in
firing and entrained flow gasification simulation.
metal storage vessels, where it is allowed to cool down under a nitrogen
The flat flame gas burner consists of two concentric sub-burners viz.
purge. The start torrefaction temperature for the pelletized materials
a primary, inner burner (∼1 cm ID) and a secondary, outer burner
was determined to be 230 °C, but due to the exothermal behavior of the
(∼6 cm ID). A tertiary nitrogen flow is applied to create suitable mixing
materials at this temperature range (230–250 °C) the final temperatures
profiles and for thermal protection of the reactor tube. Fuel particles are
reached between 250 and 280 °C. The torrefaction process in the cur-
fed through the inner burner and are rapidly heated (> 105 °C/s) to the
rent work involved no oxygen addition, although the possibility exists.
high temperature level of, e.g., a coal flame (1400–1600 °C). The fuel
The mechanism of exothermic behavior during the biomass thermal
particles are fed by means of a commercial rotating brush/ram feeder.
decomposition process is well described in literature [5]. During tor-
The fuel feed is controlled by a piston press that transports the powder
refaction at a given temperature, the thermal behavior of biomass
to a rapidly rotating brush. The particles are dispersed by the brush and
materials is dependent on the balance between endothermic pyrolysis
transported into the reactor pneumatically. Typically, low particle feed
reactions of cellulose and exothermic pyrolysis reaction of hemi-
rates (3 g/h in the current study) are used in order to control the gas-
cellulose and lignin. Generally, a higher content of lignin in biomass
eous environment of each particle by means of the imposed gas burner
leads to higher exothermicity in biomass decomposition processes [33].
conditions. For low-NOX operation, this implies that heating and de-
Moreover, the char yield also plays a major role to change the thermal
volatilization of the fuel particles takes place in an oxygen-deficient
behavior of cellulose decomposition, leading to exothermicity if the
zone (indicated as I in Fig. 1) provided by the primary, inner burner,

Fig. 1. Staged flat flame gas burner and reactor (drop) tube in the lab-scale combustion simulator (LCS).

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P. Abelha, et al.
Fig. 2. Typical LCS temperature/residence time profile used under burner-staged low-NOX combustion mode.
whereas subsequent char combustion takes place in a zone with excess
oxygen (indicated as II in Fig. 1). The transition from oxygen-lean to
oxygen-rich takes place by diffusion and is completed at the end of zone
I. The resulting gas/particle flow is then sucked into a 76 mm ID alu-
mina reactor tube for complete oxidation of the fuel. The tube is sur-
rounded by three 3.4 kW electrically heated zones equipped with
Kanthal Super 1800 elements with a maximum element temperature of
1700 °C. The temperature of each zone is independently controlled by a
Eurotherm controller and two S-type thermocouples. A typical tem-
perature/residence time profile is shown in Fig. 2.
Industrial low-NOX burner conditions are simulated by adapting the
stoichiometry of the inner burner of the LCS to the actual primary
stoichiometry of an industrial burner. After entering a furnace, fuel
particles are rapidly heated in an environment resulting from volatile
matter combustion (flue gas containing CO, H2, CO2, H2O, N2 and little
to no O2). To create a similar environment in the LCS, the primary,
inner burner is fed with a sub- or near-stoichiometric CH4/O2 mixture.
The secondary, outer burner is then fired with an excess of oxygen to
obtain a flue gas containing 3–4% oxygen. For deep-staging scenarios
the Over Fire Air simulation facility (item 8 in Fig. 1) can be deployed,
Fig. 3. Photographs of the oil-cooled, quenched gas/ash sampling probe.
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Fuel 253 (2019) 1018–1033
although this option was not used in the current work. For this work,
the burner was operated with a primary lambda of 0.85 and a total
lambda of 1.15 without further (deep) staging.
For conversion kinetics, burnout/ash and aerosol formation studies,
particle and flue gas samples can be obtained at residence times be-
tween 10 and 3000 ms, employing a vertically adjustable, oil-cooled
probe. A photograph of the tip of the probe is shown in Fig. 3.
The particles are rapidly cooled (a nitrogen/helium quench may be
used at the tip of the probe) and are collected by either a cyclone
(d50 = 3 µm), a back-up filter or – if fractionated samples are required
– a cascade impactor. The latter instrument was used for aerosol for-
mation studies. Fly ash samples were taken isokinetically employing a
Pilat Mark V cascade impactor using 11 stages (2.8–28 L/min config-
uration), under combustion conditions with residence time of ap-
proximately 2 s. Nuclepore® polycarbonate substrates were used as
particle impaction surfaces.
For slagging tests a specialized deposition probe is used, shown in
Fig. 4. Different coupons can be attached to the probe head to simulate
different deposition surfaces in terms of material, surface structure and
temperature.
The coupons may be either uncooled (ceramics) or cooled (metal
surfaces), in the latter case the surface temperature is continuously
monitored. Sampling at different gas temperatures or residence times is
accomplished by vertically adjusting the probe inside de reactor. The
coupons can be removed for further testing (e.g., corrosion) and che-
mical or microscopic analysis of the deposit. For the current study,
uncooled alumina substrates were employed. The coupon was placed at
a burner distance of 280 mm, corresponding to a residence time of
approximately 200 ms. The local gas temperature was slightly above
1400 °C. The gathered samples were subsequently analyzed by means of
SEM/EDX.
Fouling studies were also carried out by means of a horizontal de-
position probe (HDP), which can be placed at a fixed distance from the
burner. The setup is shown in Fig. 5. The HDP is used to mimic the gas/
particle flow around a single boiler tube. It is equipped with a ring-
shaped quadruple heat-flux sensor assembly and a detachable deposi-
tion substrate. While the sensor yields on-line data on the influence of
the deposit on the effective heat flux through the tube wall, the tubular
substrate is used to collect samples for off-line deposit morphology and
P. Abelha, et al.
Fig. 4. Photograph of the oil-cooled, vertical deposition probe for slagging/
fouling investigations (1 – cooling body; 2 – metal deposit coupon; 3 – ther-
mocouple channels; 4 – thermocouple; 5 – probe body; 6 – ceramic deposit
coupon (uncooled)).
Fig. 5. Photograph and schematics of the LCS horizontal heat flux/deposition probe.
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Fuel 253 (2019) 1018–1033
chemical composition studies (by means of visual/electron microscopy,
also in combination with EDX analyses).
2.4. Analytical methods
The determination of the C, H, and N content of biomass fuels has
been carried out according to EN ISO 16948:2015 by combustion and
subsequent gas-phase separation chromatography and measurement in
an elemental analyzer FLASH 2000 (Thermo Scientific). The O content
was calculated by difference.
The ash content of the biomasses has been determined according to
EN ISO 18122:2015 by determination of the loss on ignition at 550 °C
using a Nabertherm LV5/11/B180 oven.
The determination of the chlorine content of the biomass fuels has
been carried out according to EN ISO 16994:2015, applying a de-
struction step bomb combustion in oxygen (Parr 6300 Calorimeter) and
absorption in NaOH, followed by a measurement by ion chromato-
graphy (Dionex ICS-2100).
The matrix and trace elements in the biomasses have been de-
termined by multi-step pressurized digestion of the fuel with HNO3
(65%)/HF (40%)/H3BO3, followed by inductively coupled plasma
P. Abelha, et al. Fuel 253 (2019) 1018–1033

optical emission spectroscopy (ICP-OES) using a Thermo Scientific ICP-
OES ICAP 6300 duo equipment.
The determination of the chlorine content in the washing effluents
was performed by ion chromatography. The determination of the other
elements was done by ICP-OES.
A Hitachi SU70 FEG-SEM was used to make detailed micrographs of
the slagging deposits and in combination with EDX the major elements
present were quantified.
Combustion gases are measured on-line using a pre-calibrated ABB
AO2020 modular integrated system. NDIR measurement principle is
used for CO2, CO, NO, NO2 and SO2 and paramagnetic measurement
principle is used for O2.
3. Results and discussion
3.1. Impacts on fuel characteristics
Ultimate and proximate analyses of the fuels are given in Table 1. As
expected, pre-washing the fuels removed significant amounts of
chlorine and potassium, being some of the most troublesome elements
since they are involved in corrosion, slagging and fouling. Subsequent
torrefaction removed parts of the organic matrix leaving the water-in-
soluble inorganic constituents behind at higher concentrations. Inter-
estingly, the nitrogen contents of miscanthus and road side grass
slightly decreased by pre-washing and torrefaction, indicating that
parts of the fuel nitrogen must be present in water-soluble forms such as
ammonium salts or amines in the feedstock. These results agree with
other works found in literature, where decreasing N content during
leaching was also observed [20,21]. However, during torrefaction the
loss of organic matter, lean in N content, contributed to only marginal
decreases of N after washing and torrefaction. Nevertheless, a specific
energy based N content decrease was observed with all the upgraded
biomasses due to the higher calorific value after torrefaction (see
Fig. 6).
Analyses of the original samples, washed samples and washed/tor-
refied samples showed that about 90% of Cl and up to 60–80% of K can
be removed by this upgrading route; during torrefaction part of the Cl
and S are removed from the solids, while K and Na are not significantly
altered. The pre-wash step is crucial for the removal of K. Si and Ca
remain largely in the solid fraction. Post-wash seems to be a viable
route to upgrade dry-type biomasses; “straw” like material requires
more time for washing than “grass” type. More information about the
impact of the individual upgrading processes, i.e., washing and torre-
faction can be found in [26,27]. Similar high extraction levels of Cl and
K and more limited removal for S, P and Si were found by other re-
searchers as mentioned in the introduction [21–25,39].
The washing process leads to undesirably high moisture contents of
the upgraded biomass, which will demand mechanical dewatering, or
even further thermal drying. In the case of dried biomasses like most
straws (moisture of 13–15% wt), the washing step was found to be more
economically favorable if carried out after torrefaction (post-washing),
since the moisture content found in the post-washed hydrophobic tor-
refied material was about 30% wt, while the impact on the K and Cl
extraction was marginal. On the contrary, if the biomass moisture
content is high (> 60% wt), as observed in the case of the road side
grass (moisture of 70–75 %wt), the washing should be done before
torrefaction (pre-washing). Otherwise, the energy costs to dry the bio-
mass prior to torrefaction would be too high. Moreover, the water ef-
fluent may also require waste water treatment or disposal. These two
issues of course will increase the price of the upgraded feedstock. The
technical economical evaluation of this upgrading process is out of the
scope of this work but more information on this issue can be found
elsewhere [38].
3.2. Impacts on NOX formation
The measured NOX formation of the untreated and upgraded fuels
are shown together with the values of a reference coal in Fig. 6. The
absolute amounts of NOX formed per unit mass of fuel are specific to the
air staging conditions applied in the LCS. For the values shown below,
burner staging with a primary lambda of 0.85 and a total lambda of
1.15 without further (deep) staging was applied. Hence, the reported
values are specific for these conditions. The measurements were carried
out in a two-step procedure. First, gas/particle samples were taken at a
short burner distance at which devolatilisation and subsequent volatile
matter conversion was completed, yielding a NOx concentration that is
referred to primary NOx in the following. In the second step, the mea-
surement is repeated at a longer burner distance where char conversion

Table 1
Ultimate and proximate analysis of the investigated fuels (RSG = road side grass).
Biomass material wheat straw wheat straw, upgraded miscanthus miscanthus, upgraded spruce bark spruce bark, upgraded RSG RSG, upgraded

Parameter Unit
ash (550 °C) [wt.-%, dry] 10.3 9.3 2.1 3.1 3.4 4 18.1 14.8
ash (815 °C) [wt.-%, dry] 10.2 8.8 2 2.8 3.2 3.5 16.9 14.1
volatile matter [wt.-%, dry] 71.8 70.9 81.7 75.7 74.5 69.2 66.1 61.5
HHV [MJ/kg, dry] 17.5 19.2 19.3 20.4 19.9 21.5 16.5 20
carbon [wt.-%, dry] 42.9 47.7 47.7 50.1 49.4 54.3 41.4 49.9
nitrogen [wt.-%, dry] 0.4 0.4 0.3 0.2 0.4 0.4 1.8 1.7
hydrogen [wt.-%, dry] 5.6 5.5 5.9 5.6 5.8 5.6 5.3 5.3
oxygen [wt.-%, dry] 38.6 35.9 43.3 38.9 40.2 36.2 35.4 30.7
chlorine [mg/kg, dry] 2800 540 1300 420 100 88 9500 1300
Al [mg/kg, dry] 45 180 79 160 470 580 1700 1400
B [mg/kg, dry] 1.8 2 1.9 12 11 11 40 15
Ba [mg/kg, dry] 0.73 6.8 8.2 4.4 220 250 25 33
Ca [mg/kg, dry] 2800 3800 1000 1700 11,000 14,000 18,000 13,000
Fe [mg/kg, dry] 49 250 61 330 280 370 1800 1400
K [mg/kg, dry] 8400 3400 2300 1800 2000 1000 17,000 4400
Mg [mg/kg, dry] 560 560 360 420 810 850 2000 1600
Mn [mg/kg, dry] 17 42 22 15 650 680 530 140
Na [mg/kg, dry] 140 440 260 470 160 500 1600 1000
P [mg/kg, dry] 830 610 220 250 510 430 4000 2200
S [mg/kg, dry] 820 520 480 360 330 310 3400 1400
Si [mg/kg, dry] 36,000 34,000 6500 14,000 1900 2300 45,000 46,000
Sr [mg/kg, dry] 11 23 5.3 10 44 55 91 55
Ti [mg/kg, dry] 350 41 220 18 120 87 930 220
Zn [mg/kg, dry] 6.4 29 9.1 50 140 170 39 78

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P. Abelha, et al. Fuel 253 (2019) 1018–1033

Fig. 6. Specific fuel nitrogen content and specific NOX formation: Primary NOX – formed during volatiles combustion; Secondary NOX – formed during char
combustion.

Fig. 9. Particle size distribution of untreated and upgraded spruce bark fly ash.
Fig. 7. Particle size distribution of untreated and upgraded wheat straw fly ash.

Fig. 8. Particle size distribution of untreated and upgraded miscanthus fly ash. Fig. 10. Particle size distribution of untreated and upgraded road side grass fly
ash.

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P. Abelha, et al. Fuel 253 (2019) 1018–1033

is essentially completed and the final NOx concentration after conver-
sion is recorded. By subtracting the NOx formed by the gas flame
(without solid feed) and performing mass balances for NOx in the re-
actor, the secondary NOx originating from char-bond nitrogen was
calculated by subtracting the primary NOx formed from the final NOx.
Then the total masses of NOx (primary and secondary) were referred to
the total mass of fuel fed during the experiments. By presenting the data
in this way, it is possible to make a distinction between primary NOX
generated during the combustion of volatiles and secondary NOX
formed during char combustion, assuming that the volatile-N conver-
sion is much faster than the char-N conversion during the pyrolysis and
volatile combustion step, during which the primary NOx value was
determined. With this distinction, it is possible to estimate the potential
of further (deep) air staging, since this technique offer the possibility to
further reduce primary NOX.
As expected, the road side grass samples formed the highest specific
NOX. On the other hand, these samples also show the highest potential
of absolute primary NOX reduction since the road side grass samples
form the highest amount of primary NOx which can be significantly
reduced by air staging techniques, effectively reducing the primary NOx
formation. Nevertheless, it seems unlikely that road side grass can lead
to direct NOX reduction when co-fired with coal because of the large
amount of secondary NOx formed during char combustion that even
exceeds the secondary NOx formed by the reference coal shown in
Fig. 6, unlike the other fuels under investigation (Fig. 6). Moreover, if
road side grass is to be combusted stand-alone, it seems that secondary
measures for NOX reduction, such as SCR or SNCR systems, have to be
implemented to ensure compliance with legal limits. These observa-
tions are in line with the findings from other works [40]. For all the
other biomasses NOX formation seems not to be a problem and the
general effect of upgrading is a decreasing tendency for NOX formation
with the exception of spruce bark.
Upgraded miscanthus yielded the lowest specific LCS NOX forma-
tion. The latter is in line with the specific nitrogen content of the fuel.
According to the specific nitrogen contents of spruce bark and wheat
straw, one would expect that upgraded spruce bark produces slightly
less NOX than upgraded wheat straw. However, the opposite is the case.
While the original fuels produce similar amounts of primary NOX, up-
graded spruce bark produces significantly more secondary NOX, which
is probably due to differences in nitrogen species in the fuels as well as
different distribution of volatile-N and char-N [50]. Moreover, the
higher fuel-Ca content, which was increased after upgrading can par-
tially explain this behavior since Ca is known to catalyze NOX formation
reactions [41,42]. Overall, it can be seen that the specific nitrogen
content of a fuel gives indications on how the fuel will perform but the
total NOX formation is also strongly influenced by other fuel-specific
parameters as mentioned above. A more complete overview on NOX
formation can be found here [51].
3.3. Impacts on submicron particles formation

Table 2 Fly ash samples that were taken in the LCS with a Pilat Mark V
Reduction of sub-micron particles formation after upgrading, expressed as mass
cascade impactor under combustion conditions with residence time of
per fuel energy input (percentage of initial formation).
approximately 2 s were analyzed for the particle size distribution, as
Biomass material Cumulative mass of Submicron particles shown in Figs. 7 through 10. The purpose of these measurements was to
submicron particle formation formation reduction (%)
investigate the impact of pre-washing and torrefaction on the formation
(g/GJ)
of sub-micron particles (aerosols) that can cause fouling and corrosion
straw 57.1 – problems and can affect the operation of electrostatic precipitators and
straw upgraded 17.8 68.8 flue gas cleaning in thermal power plants [43]. The latter is particularly
miscanthus 33.4 – true when the aerosols are formed by homogenous nucleation of alkali
miscanthus 15.2 54.5
upgraded
salt vapors in the flue gas and through the release of very fine CaO
bark 21.8 – particles [17,44]. In grass and straw like materials, usually the aerosol
bark upgraded 13.8 36.7 formation is dominated by K compounds, namely KCl. If S is present in
grass 129.0 – the fuel, KSO4 is formed preferentially and the Cl remains mainly in the
grass upgraded 18.0 86.0
gas phase as HCl and not in the deposits formed in the heat transfer
surfaces, reducing the high temperature corrosion risk. Other possible

Fig. 11. Alkali indices of the investigated fuels and limits as proposed in [45].

1025
P. Abelha, et al. Fuel 253 (2019) 1018–1033

aerosol species are K phosphates and carbonates. Since large amounts of kg 106 %Ash %K2 O + %Na2 O
Alkali index = × ×
alkalis and chlorine are removed during upgrading, it is expected that a
significant reduction in fine particulate matter formation can be ob-
GJ HHV ( )kJ
kg
100 100
(1)
served.
Table 2 gives an overview of the achieved fine particulate emission where HHV is the high heating value and %Ash is the ash percentage in
reduction by upgrading. After upgrading, sub-micron particles of spruce the fuel. The sum of the alkali metal oxides (%K2O and %Na2O) is re-
bark and miscanthus can be reduced by approximately 37 and 54% by ported as % of the ash content. Miles et al. [45] have suggested that
mass, respectively, while the emissions of straw and grass can even be fouling is probable for an Alkali Index above 0.17 kg/GJ and that
reduced by approximately 69 and 87%, respectively. These values are fouling virtually certain to occur for an Alkali Index above 0.34 kg/GJ.
very promising given that fine particulate fouling problems are a big The Alkali Index is incomplete as a descriptor of fouling behavior,
concern when firing fast growing biomass. The reduction on the aerosol however, it is useful principally as a general guide [46]. Nevertheless, it
formation of upgraded spruce bark is less pronounced than for the other
samples. The reason for the lower reduction in case of spruce bark is
that woody biomass forms predominantly sub-micron particles com-
posed of calcium oxide, originating from the combustion of calcium
oxalate. Since calcium oxalate is hardly water-soluble, it was not re-
moved during the pre-washing step. Further analysis of the chemical
composition of the individual cascade impactor stage samples could
shed light into the nature of the particulate matter.

3.4. Impacts on fouling tendency

The alkali index of the individual fuels is shown in Fig. 11. The
alkali index is a measure common used for biomass to predict the
fouling propensity of a fuel originating from alkali salt deposition on
heat exchangers and was calculated using the following equation [45]:

Fig. 13. Specific chlorine content of the investigated fuels.

Fig. 12. Fouling sample and the fouling factor measurements of the investigated fuels.

1026
P. Abelha, et al. Fuel 253 (2019) 1018–1033

must be refered that in case of using alumino-silicate base aditives, as
kaolin or coal ash, the Alkali Index is not aplicable at all.
It can be seen that all fuels profit greatly from the potassium re-
moval during the pre-washing. Especially spruce bark shows only a
marginal fouling propensity after pre-washing if only the alkali index is
concerned. While miscanthus also shows a low alkali index, both wheat
straw and road side grass are probably causing fouling problems even
after upgrading. However, it should be noted that the alkali index is a
very specific alkali salts deposition oriented index that makes no
statements about fine particulate matter induced fouling for instance

Fig. 14. SEM/EDX analysis of the cross section cut of the substrate fouling deposit obtained with the road side grass.

Fig. 15. SEM/EDX analysis of the cross section cut of the substrate fouling deposit obtained with the upgraded road side grass.

1027
P. Abelha, et al.
induced due the presence of sub-micron calcium oxide particles com-
monly experienced in woody biomass combustion, see also Section 3.3
on realistic aerosol formation measurements of the fuels.
Fouling studies were carried out by means of a horizontal deposition
probe (HDP), which was placed at a fixed distance from the burner
corresponding to a residence time of approximately 2.5 s. An example
of a typical fouling deposit is given in Fig. 12. The fouling factor, as
measured with this probe, is also depicted in Fig. 12 for the four bio-
mass samples and the respective four upgraded materials.
Among the four original untreated materials, wheat straw showed
the highest fouling tendency followed by the road side grass. The spe-
cific fouling factor (taken as the slope of the straight lines in Fig. 12) of
untreated wheat straw was roughly two times higher than the one of
road side grass. This is surprising considering that the grass produced a
higher load of submicron particles and has a higher alkali index. Both
miscanthus and spruce bark showed equally lower level of fouling
tendency.
As confirmed during the submicron particle measurements, the
fouling tendency is significantly decreased after the removal of the al-
kalis in the washing step. Except for the bark that showed a neutral
behavior, all the other biomasses presented a decrease in specific
fouling factor after the upgrading process. In the case of road side grass,
the upgrading process contributed to a decrease in the specific fouling
factor of about six times and for wheat straw the effect was a benefit of
a twofold decrease.
Fig. 16. Photographs of wheat straw slagging deposits.
Fig. 17. SEM/EDX analysis of wheat straw deposits.
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Fuel 253 (2019) 1018–1033
3.5. Impacts on high temperature chlorine corrosion
High temperature chlorine corrosion is mostly due to the presence
of Cl in the deposits formed on the heat transfer surfaces [47,48] as
simulated in the HDP measurements used for the fouling propensity
determination and directly related to the fuel composition and chemical
reactions that take place involving the alkalis, Cl, S, aluminosilicates
and the total amount of fly ash particles created during conversion. The
chlorine reduction both due to pre-washing and torrefaction yields for
wheat straw and miscanthus very similar specific chlorine contents of
30 and 22 mg/MJ, respectively, while spruce bark yields a very low
value of 4 mg/MJ of specific chlorine content (Fig. 13). Even the very
chlorine rich road side grass yields a value of 69 mg/MJ after up-
grading. Obviously, these high removal yields are due to the fact that
chlorine is mostly present in water-soluble form and can hence be re-
moved efficiently. The achieved values indicate that high temperature
chlorine corrosion is expected to be significantly reduced for the up-
graded materials. However, the Cl content of the upgraded road side
grass can still pose a moderate risk of high temperature chlorine in-
duced corrosion.
The cross section of the deposits of the fouling tests were analyzed
by SEM/EDX and the results of the tests carried out with the road side
grass, as well as the upgraded road side grass are depicted in Figs. 14
and 15. The road side grass was selected for this analysis because it
represented the worst case scenario in terms of expected high tem-
perature corrosion and confirmed the benefits of the higher Cl and al-
kali removal during upgrading. The metal substrate surface can be ea-
sily recognized in the elemental mapping of the substrate – by Cr (blue)
and Ni (pink), shown in the bottom right part of Figs. 14 and 15. The
substrate/deposit interface can be seen in the bottom part of each in-
dividual picture right above the rich Cr and Ni zone. The composition of
the deposit could be roughly evaluated and is also presented. The de-
posit of the upgraded grass (Fig. 15) is depleted in Cl and K when
compared to the deposit composition of the original grass (Fig. 14), as
expected. However, the major difference can be found on the interface
of the metal surface. In case of the untreated grass (Fig. 14), a thin layer
of K associated also with Cl has developed on the surface of the metal
substrate, either due to direct condensation of KCl vapors, or deposition
of the potassium chloride aerosols. The latter phenomena are the major
mechanisms to promote high temperature chlorine corrosion at the
surface of heat exchangers. On the contrary, in the case of upgraded
grass, such thin layer of K and Cl is completely absent indicating a
significant reduction in the potential for high temperature corrosion.
Nevertheless, even after upgrading, still some Cl was found at some
located spots at the metal surface and therefore high temperature
chlorine corrosion cannot be completely ruled out.
P. Abelha, et al.
3.6. Impacts on near-burner slagging
Slagging tendencies of fuels are often assessed by fuel indices and
indicators, often derived for fossil fuel ash. However, they often fail to
predict the true slagging propensities of the biomass fuels since the
Fig. 18. Photographs of miscanthus slagging deposits.
Fig. 19. SEM/EDX analysis of miscanthus deposits.
1029
Fuel 253 (2019) 1018–1033
occurrence of specific phases and minerals containing problematic
elements are not accounted for [49]. Therefore, live combustion de-
posits under conditions resembling near-burner environments were
carried in order to shed light into the true nature of deposit formation of
the fuels under investigation.
Photographs of wheat straw slagging samples taken with the ver-
tical deposition probe, both with untreated and upgraded materials, are
shown in Fig. 16. Both fuels created a rather fluffy, highly sintered
deposit that was growing several millimeters in height. The deposit of
the upgraded wheat straw appears to be slightly darker in color than the
untreated material, which is probably due to a different deposit mor-
phology. The two deposits were further analyzed by SEM/EDX analysis
in order to shed light into the morphology and the composition of the
deposits. The SEM magnification of the untreated and upgraded wheat
straw deposits is presented in Fig. 17. Even though the morphology
does not differ strongly, it can clearly be seen than the deposited par-
ticles from the upgraded wheat straw are finer than from the untreated
material. The latter allows for a denser packing of the particles which in
turn explains the darker color of the deposit. Also under this magnifi-
cation it is clearly visible that individual particles are sintered together
and form a porous solid network, i.e. no molten slag is formed. The
chemical composition of selected regions of the deposits is given in
Fig. 17. The SEM/EDX analysis reveals that the composition of the
deposits is fairly homogeneous for both samples. The most remarkable
P. Abelha, et al.
difference is the reduction in potassium by roughly 50% in the deposit
of the upgraded wheat straw sample, which was anticipated due to the
pre-washing. It appears that calcium silicates form the basis for the
sintering of the particles, while glass-type alkali silicates appear to play
a minor role. Overall, it can be concluded that pre-washing of wheat
straw has minor effect on the slagging propensity of the feedstock.
However, for none of the two cases, molten running slag could be ob-
served and hence the slagging risk for the fuels should be considered
moderate.
The deposits collected with the untreated and upgraded miscanthus
differ visually little from the ones collected from wheat straw. They
appear very fluffy, consisting of highly sintered individual particles
(Fig. 18). Like for the wheat straw case, also the upgraded miscanthus
deposit is darker in color and significantly larger in size compared to
the untreated material. However, when taking a look at the SEM
magnifications (Fig. 19), distinct differences compared to the wheat
straw deposits are visible. In case of miscanthus, more molten particles
are observable. Nonetheless, also untreated and upgraded miscanthus
form a solid porous network of sintered particles, i.e. no running slag is
formed. Interestingly, also the upgraded miscanthus forms a deposit
that is made up of significantly finer material than the untreated
feedstock. The underlaying reasons for this difference in morphology
are yet to be investigated. Most probably the silica based skeleton of the
original materials is desegregated into smaller size particles during the
thermal treatment in the torrefaction step. Therefore, smaller silica
based particles must be impacting and building up a deposit with a
more packed slag layer, in the case of these particular torrefied mate-
rials.
Magnifications of the SEM micrographs of the miscanthus deposits
are given in Fig. 19. Only with the higher magnification the true extent
of melting can be visualized. In case of untreated miscanthus
Fig. 20. Photographs of roadside grass slagging deposits.
Fig. 21. SEM/EDX analysis of roadside grass deposits.
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Fuel 253 (2019) 1018–1033
completely molten particles made up of alkali and calcium silicates (see
EDX spectra 115 and 116 in Fig. 19) were found in the deposit. The
partially molten particles of upgraded miscanthus are made up of cal-
cium silicates with significantly lower concentrations of potassium. The
latter is most likely the reason for the higher melting temperatures of
the ashes. Pre-washing of miscanthus results in a reduced slagging
propensity because the fully molten particles are expected to form a
higher risk, despite the increased height of the deposit created with
upgraded miscanthus. Nonetheless, also upgraded miscanthus still ex-
poses a moderate slagging risk.
Photographs of the collected slagging samples produced of road side
grass are given in Fig. 20. The untreated road side grass formed a fully
molten deposit, while the upgraded material created a highly sintered
deposit in which individual particles are still visible. Evidently, the
visual impact of pre-washing is the strongest for the road side grass if
the slagging propensity is concerned.
However, the SEM micrographs reveal that the improvement with
upgraded road side grass is not as promising as expected from the visual
inspection. The top layer of the deposit, where temperatures are the
highest, shows initial melting of the material (Fig. 21). The SEM/EDX
micrographs of the deposits of roadside grass offer insight into the
chemical composition. The molten deposit of untreated road side grass
is very homogeneous and is made up of calcium silicates with sizeable
amounts of potassium. The trapped particles are either sand or calcium
oxide units originating from limestone present in the fuel. The com-
position of the deposit of the upgraded material differs only marginally
from the untreated one with the exception of a halved potassium con-
centration.
The latter underlines the fact that even small alterations of po-
tassium content can have measurable impact on the melting behavior of
an ash. Overall it can be concluded that both road side grass samples
expose a severe slagging risk when fired in a pulverized fuel
Fig. 22. Photographs of spruce bark slagging deposits.
P. Abelha, et al.
installation.
The case of spruce bark is completely different from the other bio-
masses tested. Unlike the other fuels under investigation, both un-
treated and upgraded spruce bark formed a loose black-brown deposit
with no signs of sintering or melting, at least not visible with the naked
eye, as depicted in Fig. 22.
Also the SEM micrographs in Fig. 23 reveal that only loose deposits
are formed with few partially molten particles. Overall, the deposit
morphologies resemble the ones seen for wood firing in earlier tests
carried out at ECN part of TNO. In case of spruce bark, the deposit
chemistry is dominated by calcium containing species, mainly calcium
oxide, which explains why only very little material was deposited, be-
cause the melting point of calcium oxide is very high (> 2500 °C).
Those few particles that are partially molten generally show enriched
silica contents, but also enrichments of phosphorous and/or iron and
manganese, see EDX spectra 95, 100 and 101 in Fig. 23. Those ele-
ments, in particular silica and iron are prone to form lower melting
eutectics with calcium which explains the partially molten nature of the
particles. Composition wise, the two deposits differ overall mainly in
the calcium content, which is approximately 2%-wt. lower for the up-
graded sample. Overall, the two materials can be considered to expose a
low slagging risk for boiler operation.
In summary, it can be concluded that only the spruce bark samples
Fig. 23. SEM/EDX analysis of spruce bark deposits.
1031
Fuel 253 (2019) 1018–1033
are expected to have a low slagging propensity when fired in a pul-
verized fuel boiler. Both the upgraded wheat straw and the miscanthus
samples expose a moderate slagging propensity. However, pre-washing
and torrefaction apparently alters the fuels in such way that the created
deposits are formed by smaller particles and consequently form a
denser packed deposit which can have impact on the heat transfer
through the deposit. Road side grass, even if upgraded, appears to be a
highly slagging fuel due to the still intense melting of the ash.
Pre-washing of the feedstocks alone seems not to be an adequate
measure in order to substantially suppress slagging. The addition of
mineral combustion additives or smart fuel blending might be necessary
steps in order to mitigate the slagging risks even further.
4. Conclusions
Standard lab-analysis combustion experiments in a PF Lab-Scale
Combustion and Gasification Simulator were performed to investigate
the fuel quality improvements through pre-washing and torrefaction
during combustion. Four fuels were tested, namely wheat straw, mis-
canthus, spruce bark and road side grass.
From the elemental composition of the upgraded fuels it can be
concluded that high temperature chlorine corrosion can be effectively
reduced since chlorine concentrations are reduced to non-critical values
P. Abelha, et al.
(Fuel-Cl < 30 mg/MJ) except for road side grass that still exposes
significant corrosion risk (Fuel-Cl = 69 mg/MJ) and Cl was still fount in
the interface of the deposit and the metal surface of the simulated heat
exchanger. The removal of alkalis (up to 76% on energy basis) is
equally effective, effectively reducing the risk of alkali induced fouling.
Moreover, both K and Cl concentrations measured at the interface of a
simulated heat exchanger surface and the deposits are significantly
decreased after upgrading the biomasses. Moreover, fine particulate
matter formation is strongly reduced by upgrading the fuels, and
therewith – alongside with lower aerosol formation – the risk of alkali-
induced/fine particulate matter fouling is minimized effectively. The
actual expected fouling reduction level after upgrading is fuel-specific,
being 37% for bark and 86% for grass.
Slagging tests revealed that pre-washing and torrefaction has minor
impact on the slagging propensity of the fuel. However, slightly reduced
slagging is observable. Nevertheless, with the exception of spruce bark,
the fuels under investigation still expose slagging risks to full scale
operation.
The generally observed increase in NOX formation due to torrefac-
tion is compensated by partial removal of fuel nitrogen during pre-
washing. After upgrading, the fuel-N was reduced between 10% (straw)
and 37% (miscanthus), on an energy basis. Wheat straw, miscanthus
and spruce bark have a potential for direct primary NOX reduction
when co-fired with coal. Road side grass will most likely require ad-
ditional NOX reduction measures when co-fired with coal due to its high
fuel nitrogen content and unfavorable distribution of volatile-N and
char-N.
It can be concluded that pre-washing and torrefaction can greatly
improve fuel quality both in terms of handling and storage improve-
ments and also when combustion related aspects are concerned.
However, it was demonstrated that slagging mitigation will most likely
be required for all of the fuels except for spruce bark. Effective slagging
suppression can be achieved by means of mineral combustion additives.
Alternatively, smart blending with other fuels might be an option.
Acknowledgements
Research funded by the Dutch Ministry of Economic Affairs (Tender
1 BBE – KEW project TEBE214004), The Netherlands and the European
Union’s Horizon 2020 research and innovation programme under grant
agreement No. 727616.
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