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Fuel 158 (2015) 330350

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Review article

Advantages and disadvantages of composition and properties of biomass


in comparison with coal: An overview
Stanislav V. Vassilev a,, Christina G. Vassileva a, Vassil S. Vassilev b
a
b

Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, Block 107, Soa 1113, Bulgaria
Space Research and Technology Institute, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, Block 1, Soa 1113, Bulgaria

h i g h l i g h t s
 Composition and properties of biomass were summarised.
 Comparative characterization between biomass and coal was given.
 Advantages of biomass composition and properties were described.
 Disadvantages of biomass composition and properties were discussed.

a r t i c l e

i n f o

Article history:
Received 23 February 2015
Received in revised form 22 April 2015
Accepted 19 May 2015
Available online 30 May 2015
Keywords:
Biomass
Coal
Ash
Composition and properties
Advantages and disadvantages

a b s t r a c t
An extended overview of the advantages and disadvantages of biomass composition and properties for
biofuel application was conducted based on reference peer-reviewed data plus own investigations.
Initially, some general considerations and comparisons about composition and properties of biomass
and coal as the most popular solid fuel are addressed. Then, some of the major advantages related to
the composition and properties of biomass and/or biomass ash (BA) are discussed. They include: (1) high
values of volatile matter, H, structural organic components, extractives and reactivity of biomass,
water-soluble nutrient elements and alkaline-earth elements in biomass and BA, and pH of BA; and (2)
low values of C, xed C, ash, N, S, Si and initial ignition and combustion temperatures of biomass, and
low contents of many trace elements including hazardous ones in biomass and BA. Further, some of
the major disadvantages connected with the composition and properties of biomass and/or BA are
described. They comprise: (1) high values of moisture and O in biomass, water-soluble fraction, alkaline
and halogen elements, and some hazardous trace elements in biomass and BA; (2) low values of energy
density (bulk density and caloric value), pH and ash-fusion temperatures of biomass, and bulk density
and size of BA; (3) highly variable composition and properties of biomass and BA; and (4) indenite availability of sustainable biomass resources for production of biofuels. Finally, a discussion about the availability of sustainable biomass resources for production of biofuels and biochemicals is given. It was found
that the disadvantages of biomass for biofuel and biochemical applications prevail over the advantages;
however, the major environmental, economic and social benets appear to compensate the technological
and other barriers caused by the unfavourable composition and properties of biomass.
2015 Elsevier Ltd. All rights reserved.

Contents
1.
2.
3.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Materials, methods and data used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
General considerations and comparisons about composition and properties of biomass and coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Advantages of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.1.
Volatile matter, combustion temperatures and reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Corresponding author. Tel.: +359 2 9797055; fax: +359 2 9797056.


E-mail address: vassilev_stan@yahoo.com (S.V. Vassilev).
http://dx.doi.org/10.1016/j.fuel.2015.05.050
0016-2361/ 2015 Elsevier Ltd. All rights reserved.

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S.V. Vassilev et al. / Fuel 158 (2015) 330350

4.

3.2.2.
Carbon, fixed carbon and hydrogen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.3.
Structural organic components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.4.
Extractives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.5.
Ash yield and inorganic matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.6.
Water-soluble nutrient elements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.7.
Alkaline-earth elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.8.
Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.9.
Sulphur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.10.
Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.11.
Trace elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.12.
pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Disadvantages of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.1.
Moisture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.2.
Alkaline and halogen elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.3.
Hazardous trace elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.4.
Ash-fusion temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.5.
Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.6.
Energy density, bulk density and calorific value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.7.
Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.8.
Variable composition and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.9.
Sustainable biomass resources. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

331

337
337
338
338
340
341
342
342
343
343
343
343
343
343
344
346
346
346
347
347
347
348
348

Nomenclature
A
AFT
BA
daf
db
DTA
DWR
EDX
FC
HHV
IAM
ICP

ash yield
ash-fusion temperature
biomass ash
dry, ash-free basis
dry basis
differential-thermal analysis
dry water-soluble residue
energy dispersive X-ray analyser
xed carbon
higher heating value
inorganic amorphous matter
inductively coupled plasma

1. Introduction
Biomass can be converted into solid, liquid and gaseous biofuels
for generating bioenergy, as well as into some chemicals. It is
widely accepted that biofuels combustion does not contribute to
the greenhouse effect due to the CO2 neutral conversion thanks
to the renewability of biomass. The focus on bioenergy as an alternative to fossil energy has increased tremendously in recent times
because of global warming problems originating mostly from fossil
fuels combustion. Therefore, extensive investigations have been
carried out worldwide recently to enhance biomass use instead
of fossil fuels for energy production ([17] and references therein).
Numerous biomass varieties among biomass groups, namely wood
and woody biomass, herbaceous and agricultural biomass, aquatic
biomass, animal and human biomass wastes, semi-biomass (contaminated biomass and industrial biomass wastes such as municipal solid waste, refuse-derived fuel, sewage sludge, demolition
wood and other industrial organic wastes) and their biomass mixtures can be used for biofuels and biochemicals [1,2]. In total about
9597% of the worlds bioenergy is currently produced by direct
combustion of biomass and the perspective of increasing
large-scale combustion of natural biomass and its co-combustion
with semi-biomass and solid fossil fuels (coal, peat, petroleum
coke) seems to be one of the main drivers for biofuel promotion

IM
LA
M
MS
OM
SEM
TE
TGA
VM
XRD
%

inorganic matter
laser ablation
moisture
mass spectrometry
organic matter
scanning electron microscopy
trace element
thermo-gravimetric analysis
volatile matter
X-ray powder diffraction
weight%

in many countries worldwide in the near future ([3] and references


therein).
Two fundamental aspects related to biomass use as fuel are: (1)
to extend and improve the basic knowledge on composition and
properties; and (2) to apply this knowledge for the most advanced
and sustainable utilisation of biomass. The fuel composition is a
fundamental code that depends on various factors and denite
properties, quality and application perspectives, as well as different technological and environmental problems related to any fuel
[1]. Therefore, extensive reference peer-reviewed data plus own
investigations for both biomass and biomass ash systems were
used recently to perform several extended and consecutive overviews related to: (1) chemical composition of biomass [1]; (2)
organic and inorganic phase composition of biomass [2]; (3)
phase-mineral and chemical composition of biomass ash (BA)
[3]; (4) potential utilisation, technological and ecological advantages and challenges of BA [4]; and (5) behaviour of biomass during
combustion, namely phase-mineral transformations of organic and
inorganic matter [5] and ash-fusion and ash-formation mechanisms of biomass types [6]. New classications based on data from
proximate, ultimate, ash, structural and mineralogical analyses,
and ash-fusion tests of biomass or BA have been introduced therein
[16]. Additional investigations on trace element concentrations
and associations in biomass and BA have also been conducted

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S.V. Vassilev et al. / Fuel 158 (2015) 330350

[7]. It was highlighted in the above studies that there are different
advantages and disadvantages related to biomass composition and
properties for fuel application and they have very important ecological and technological impacts during sustainable utilisation of
biomass fuels and their products.
Studies connected with advantages and disadvantages of using
biomass fuels for thermochemical (combustion, pyrolysis, gasication and liquefaction) and biochemical (anaerobic digestion, alcoholic fermentation, aerobic biodegradation) conversions, as well
as co-combustion, co-pyrolysis and co-gasication of biomass with
other solid fuels have been performed worldwide ([148] among
others). As a result, substantial data for the composition and properties of biomass, biochar and BAs such as low-temperature and
high-temperature laboratory ashes and industrial bottom ashes,
slags and y ashes, along with the behaviour of different biomass
varieties during their thermal treatment have been generated
and summarised recently [17]. Some comparative characterizations between biomass and other fossil fuels have also been given
in some of the above investigations. It is well known that the
methodology and logic from coal experiments can be applied to
biomass [8]. However, parallel and detail comparisons between
biomass and coal as the most popular solid fuel, as well as their
respective conversion products based on numerous characteristics,
namely: (1) chemical composition (major, minor and trace elements); (2) phase-mineral composition of organic matter (cellulose, hemicellulose, lignin, extractives, petrographic ingredients,
char) and inorganic matter (mineral classes, groups and species,
and inorganic phases); and (3) various properties (volatile matter,
xed C, moisture, ash yield, ash-fusion and combustion temperatures, density, pH, caloric value and water-soluble components);
are still limited. Therefore, an attempt to summarise the advantages and disadvantages of the above characteristics based on the
data from numerous combined investigations for both biomass
and coal was undertaken and is described below.
The major aims of the present overview are: (1) to systematize
and summarise the peer-reviewed data; (2) to supply additional
own results; (3) to describe some basic ndings; and (4) to clarify
the advantages and disadvantages related to the biomass composition and properties compared to coal as a traditional and conventional fossil fuel. Indications of some potential technological and
environmental challenges during processing of biomass fuels, as
well as application of their products are also addressed.
2. Materials, methods and data used
The summarised data for the composition and properties of biomass and coal based on own data-base including numerous mostly
peer-reviewed publications (totally more than 840 references)
have been used for the present and former overviews ([16] and
references therein). Additionally, eight biomass samples (beech
wood chips, corn cobs, marine macroalgae, plum pits, rice husks,
switchgrass, sunower shells and walnut shells) were collected
and studied in detail for the determination and elucidation of
many characteristics related to the chemical and phasemineral
composition of biomass and BA, and behaviour of biomass during
combustion [27]. The samples investigated belong to different
biomass groups and sub-groups classied by origin (biodiversity
and source), as well as to variable organic and inorganic types
and sub-types specied for biomass and BA [13,6]. These biomass
samples were studied using methods such as light microscopy,
powder X-ray diffraction (XRD) and scanning electron microscopy
(SEM), and differential-thermal (DTA), thermo-gravimetric (TGA)
and different chemical analyses, as well as some leaching, precipitation, ashing (5001500 C) and other procedures described in
detail earlier [2,3,57].

3. Results and discussion


3.1. General considerations and comparisons about composition and
properties of biomass and coal
The composition of biomass and BA is highly variable because
each biomass and BA variety has specic origin and formation conditions, which can cause enrichment or depletion of different elements and phases [17]. For example, the composition and
properties of biomass and BA depend on many factors including:
(1) biomass resource (type of biomass, plant species or part of
plants, growing processes and conditions, age of the plants, fertilizer and pesticide doses used, harvesting time, collection technique, contamination, transport, storage, processing, others); (2)
biomass fuel preparation (pre-treatment and upgrading such as
drying, cutting-grinding, densication, and torrefaction); (3) biomass combustion (combustion technology and conditions, collection and cleaning equipment); and (4) transport and storage of
BA. It should be stated that the composition and properties of biomass and BA are much more variable than those of coal and coal
ash (Tables 1 and 2 and [17]).
The elemental composition of biomass and BA may potentially
include the entire periodic table and comprises: (1) major (>1%);
(2) minor (0.11%); and (3) trace (<0.1%) elements; according to
their contents (Tables 1 and 2). As a general trend (Table 2), most
of the elements determined in biomass are trace elements (TEs)
excluding C, Ca, Cl, H, K, Mg, N, Na, O, P and S based on the
Clarke contents (worldwide average concentrations) for angiospermous and gymnospermous plants [49] and world reference plant
(worldwide averages of all parts of all plants) [16]. On the other
hand, most of the elements detected in BA (Table 2) are also TEs
excluding Al, Ca, Cl, Fe, K, Mg, Mn, Na, O, P, Rb, S, Si, Sr and Zn based
on the Clarke contents for plant ashes [50] and world reference
plant ash [16]. Nevertheless, there are many individual cases
among biomass varieties and their ashes where the concentrations
for certain major, minor and TEs are interchanged.
A summarised comparison between the mean values of elements
and some properties for biomass and BA and those for coal and coal
ash, respectively (Tables 1 and 2, and [17,16,4952]), are listed in
Table 3. As a general trend, it can be seen from the above data that
most non-metals and especially halogen non-metals (B, Br, Cl, H, I,
O, P), alkaline and alkaline-earth lithophile elements (Ca, K, Mg,
Na, Rb, Sr), and only some chalcophile (Cu, Ga, Hg, Te, Zn), siderophile (Cr, Mn), noble (Ag, Ru) and other lithophile (Mo) elements
are commonly more enriched in biomass and BA than in coal and
coal ash, respectively. The reason for that is mostly associated with
higher amount of organic matter (OM) and limited inorganic matter
(IM) with authigenic and, to a lesser extent, detrital origin in biomass
than in coal [13,7]. In contrast, most elements among lithophile,
siderophile, chalcophile, radioactive and noble elements, and only
some non-metals (C, F, N, S, Si) are normally more enriched in coal
and coal ash than in biomass and BA, respectively (Table 3). The reason for that is mainly associated with higher amount of IM with
detrital and, to a lesser extent, authigenic nature in coal than in biomass [13,7]. For example, it is well known that the bulk amount of
ash-forming constituents in biomass based on ash yield is generally
much lower in contrast to coal (Table 1). However, the concentrations of some elements in BA can be very high due to the enhanced
enrichment factor of such elements in the combustion residue due
to the high contents of OM (cellulose, hemicellulose and lignin) in
biomass. For instance, Ag, B, Br, Ca, Cr, Cu, Ga, Hg, I, K, Mg, Mo, Na,
P, Rb, Sr, Te, Zn and others in BA can exhibit much higher enrichment
factors in comparison with coal ash (Tables 1 and 2, and [7]).
The bulk chemical composition of biomass and BA is an
important characteristic, but it is quite insufcient for a reliable

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S.V. Vassilev et al. / Fuel 158 (2015) 330350


Table 1
Mean and range values for common characteristics of coal, biomass, coal ash and biomass ash based on [17] and references therein, wt.% on air-dried basis.
Coal ash

Biomass ash

EDFa biomass/coal

Characteristic

Coal

Biomass

Proximate analysis
VM
FC
M
A
Sum

30.8 (12.244.5)
43.9 (17.970.4)
5.5 (0.420.2)
19.8 (5.048.9)
100.0

64.4 (30.479.7)
16.0 (6.535.3)
14.7 (2.562.9)
4.9 (0.134.3)
100.0

2.09
0.36
2.67
0.25

Ultimate analysis
C (daf)
O (daf)
H (daf)
N (daf)
S (daf)
Sum

78.2 (62.986.9)
13.6 (4.429.9)
5.2 (3.56.3)
1.3 (0.52.9)
1.7 (0.29.8)
100.0

51.1 (42.260.5)
41.4 (20.849.0)
6.2 (3.210.2)
1.1 (0.112.2)
0.20 (0.011.69)
100.0

0.65
3.04
1.19
0.85
0.12

EDFb biomass
ash/coal ash

Ash analysis
SiO2
CaO
K2O
P2O5
Al2O3
MgO
Fe2O3
SO3
Na2O
TiO2
Sum

54.06 (32.0468.35)
6.57 (0.4327.78)
1.60 (0.294.15)
0.50 (0.101.70)
23.18 (11.3235.23)
1.83 (0.313.98)
6.85 (0.7916.44)
3.54 (0.2714.42)
0.82 (0.092.90)
1.05 (0.621.61)
100.00

29.14 (0.0294.48)
25.99 (0.9783.46)
19.40 (2.1963.90)
5.92 (0.5440.94)
4.49 (0.1015.12)
5.60 (0.1916.21)
3.41 (0.2236.27)
3.27 (0.0114.74)
2.54 (0.0929.82)
0.24 (0.012.02)
100.00

0.54
3.96
12.13
11.84
0.19
3.06
0.50
0.92
3.10
0.23

Ash fusion test


DT (C)
HT (C)
FT (C)

1251 (11051525)
1388 (12001575)
1411 (12051585)

1103 (6701565)
1319 (9751665)
1354 (1000>1700)

0.88
0.95
0.96

800 (4001100)

194 (80430)

10.0 (6.212.5)
1.6 (0.27.2)

10.3 (8.112.9)
27.0 (3.945.1)

Other characteristics
Bulk density (kg m 3)
HHV (MJ kg 1)
Initial ignition by DTATGA (C)
Peak combustion by DTATGA (C)
pH of leachate
DWR

1250 (11001300)
25.0 (16.034.0)
256 (190322)
508 (415600)
5.9 (2.27.5)
2.1 (0.28.4)

563 (250954)
18.0 (14.022.0)
167 (144190)
339 (324351)
5.6 (5.16.8)
3.8 (0.315.1)

0.45
0.72
0.65
0.67
0.95
1.81

0.24

1.03
16.88

Abbreviations: A, ash yield; daf, dry ash-free basis; db, dry basis; DT, deformation temperature; DTA, differential-thermal analysis; DWR, dry water-soluble residue; FC, xed
carbon; FT, uid temperature; HHV, higher heating value; HT, hemispherical temperature; M, moisture; TGA, thermo-gravimetric analysis; VM, volatile matter.
a
Enrichment/depletion factor (EDF) is dened as a ratio of the value for biomass to the respective value for coal.
b
Enrichment/depletion factor (EDF) is dened as a ratio of the value for biomass ash to the respective value for coal ash.

explanation of elemental behaviour during biomass and BA


utilisation because the knowledge about the modes of element
occurrence in biomass and BA is also required for that purpose.
The abundance, origin and behaviour of modes of element occurrence (minerals and phases) in biomass and BA is a leading factor
to fully understand the above issue. The elements in biomass and
BA can occur in both OM and IM as each element has dominant
associations and afnities to specic components, phases or minerals [7]. Therefore, the phasemineral composition of biomass [2]
and BA [3] has been summarised recently. The data indicate that
the modes of element occurrence in biomass and BA can be similar
to coal and coal ash [2,3,7]. It was found that numerous minerals
and phases identied in coal and coal ash were also present in
biomass and BA. However, many mineral species among
CaKMn silicates, CaAlMn oxides, KNaCa chlorides and
KCaMgNa carbonates, sulphates and phosphates were normally
not identied in coal and coal ash. The reason for that could be
the enrichment of elements such as Ca, Cl, K, Mg, Mn, Na and P
in biomass and BA compared to coal and coal ash. In contrast, many
Al-, Fe-, Si- and Ti-bearing minerals, typical for coal and coal ash,
were not identied in biomass and BA probably due to limited
contents of these elements in biomass and BA [2,3].
The above-listed observations on the composition, as
well as some properties given in Table 3 (see below) have a
primary importance for evaluating different technological and

environmental problems or benets related to thermochemical and


biochemical conversions of biomass, coal and other solid fuels [47].
3.2. Advantages of biomass
The major advantages and disadvantages related to the use of
biomass as fuel are listed in Tables 4 and 5. It should be noted that
the benets in some cases can be barriers in other circumstances
and vice versa during biomass and biofuel application. The highly
variable composition and properties of biomass have been
described in detail [17]. Therefore, the evaluation of some key
advantages and disadvantages related to biomass and BA composition and properties in the present study is based on the mean values of many characteristics to assess the general trends compared
to coal and coal ash (Tables 13).
Most of the common advantages of biomass and biofuel related
to environmental, technological, economic and social issues
(Table 4) have been described relatively well, while the benets
connected with the composition and properties of biomass and
biofuel have been discussed to a lesser extent in the literature
[148]. Some of the major advantages related to the composition
and properties of biomass and/or BA include: (1) high values of
volatile matter (VM), H, structural organic components, extractives
and reactivity of biomass, water-soluble nutrient elements and
alkaline-earth elements in biomass and BA, and pH of BA; and

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S.V. Vassilev et al. / Fuel 158 (2015) 330350

Table 2
Clarke contents (worldwide average element concentrations) of coal, biomass, coal ash and biomass ash based on [7], ppm on dry basis.
Element

Clarke for
coalsa,b

World reference
plantc

Clarke for angiospermous


plantsd

Clarke for
gymnospermous plantse

Clarke for coal


ashesf,g

World reference
plant ashh

Clarke for plant


ashesi

Ag
Al
As
Au
B
Ba
Be
Bi
Br
C
Ca
Cd
Ce
Cl
Co
Cr
Cs
Cu
Dy
Er
Eu
F
Fe
Ga
Gd
Ge
H
Hf
Hg
Ho
I
In
Ir
K
La
Li
Lu
Mg
Mn
Mo
N
Na
Nb
Nd
Ni
O
Os
P
Pb
Pd
Pa
Pr
Pt
Rb
Re
Rh
Ru
S
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Tb
Te
Th
Ti
Tl
Tm
U

0.095a
15,000b
8.3a
0.0037a
52a
150a
1.6a
0.97a
5.2a
630,000b
4600b
0.22a
23a
180a
5.1a
16a
1.0a
16a
2.1a
0.93a
0.47a
88a
13,000b
5.8a
2.7a
2.2a
52,000b
1.2a
0.10a
0.54a
1.9a
0.031a
0.002a
1800b
11a
12a
0.20a
1100b
86a
2.2a
13,000b
800b
3.7a
12a
13a
160,000b
<0.001b
230a
7.8a
0.0074a

0.2
80
0.1
0.001
40
40
0.001
0.01
4
445,000
10,000
0.05
0.5
2000
0.2
1.5
0.2
10
0.03
0.02
0.008
2
150
0.1
0.04
0.01
65,000
0.05
0.1
0.008
3
0.001
0.0001
19,000
0.2
0.2
0.003
2000
200
0.5
25,000
150
0.05
0.2
1.5
425,000
0.000015
2000
1
0.001

0.06
550
0.2
<0.00045
50
14
<0.1
0.06
15
454,000
18,000
<0.64
<34
2000
0.48
0.23
0.2
14

0.07
65

0.61f
114,500g
47f
0.022f
335f
940f
9.4f
5.9f
32f

4.1
1633
2.0
0.02
816
816
0.02
0.2
82

1.0
14,000
0.3

35,100g
1.2f
130f
1440f
32f
100f
6.6f
92f
14f
5.5f
2.5f
605f
99,200g
33f
16f
15f

204,082
1.0
10
40,816
4.1
31
4.1
204
0.6
0.4
0.2
41
3061
2.0
0.8
0.2

8.3f
0.75f
4.0f
12.6f
0.16f
0.010f
13,700g
69f
66f
1.2f
8400g
490f
14f

1.0
2.0
0.2
61
0.02
0.002
387,755
4.1
4.1
0.06
40,816
4082
10

0.05
0.001

6100g
20f
67f
76f

3061
1.0
4.1
31

20,000
0.5

<0.008g
1350f
47f
0.037f

0.0003
40,816
20
0.02

0.0005
70,000
10

3.5a
0.035a
14a
<0.001b
<0.001b
<0.001b
18,000b
0.92a
3.9a
1.3a
27,000b
2.0a
1.1a
110a
0.28a
0.32a
<0.1b
3.3a
800a
0.63a
0.31a
2.4a

0.05
0.00005
50

20f
0.13f
79f
<0.008g
<0.008g
<0.008g
137,400g
6.3f
23f
8.8f
206,100g
13f
6.4f
740f
1.7f
2.1f
<0.8g
21f
4650f
4.9f
2.0f
16f

1.0
0.001
1020

0.021
0.5
140
0.05

63
63

450,000
6500
<0.24

0.2
0.16
15

130
<0.07

0.015
0.4

14,000
0.085
0.1

6300

3200
630
0.9
30,000
1200
0.3
<24
2.7
410,000

1300
330
0.13
32,000
340
0.3

2300
2.7

2900
1.8

1.9
440,000

400
100
2.1
0.0005
150
30,000
0.01
10,000
15
250
2.0
200

10
10,000
50

50
0.05
0.000005
30,000
11
70,000
7500
20

50

0.0005

0.0001
0.0001
3000
0.1
0.02
0.02
1000
0.04
0.2
50
0.001
0.008
0.05
0.005
5
0.05
0.004
0.01

20

0.005
3400
0.06
0.008
0.2
200
0.0055
0.3
26

1100

0.24

<0.0015

1
0.0015
0.038

<0.35

0.002
0.002
61,224
2.0
0.4
0.4
20,408
0.8
4.1
1020
0.02
0.2
1.0
0.10
102
1.0
0.08
0.2

0.000005
100
0.000005
0.00005
0.00005
50,000
0.05
0.5
150,000
5.0
30
0.005

0.5
1000
0.005
0.5

335

S.V. Vassilev et al. / Fuel 158 (2015) 330350


Table 2 (continued)

a
b
c
d
e
f
g
h
i

Element

Clarke for
coalsa,b

World reference
plantc

Clarke for angiospermous


plantsd

Clarke for
gymnospermous plantse

Clarke for coal


ashesf,g

World reference
plant ashh

Clarke for plant


ashesi

V
W
Y
Yb
Zn
Zr

25a
1.1a
8.4a
1.0a
23a
36a

0.5
0.2
0.2
0.02
50
0.1

1.6
0.07
<0.6
<0.0015
160
0.64

0.69

155f
6.9f
51f
6.2f
140f
210f

10
4.1
4.1
0.4
1020
2.0

61
0.005
10

Clarke
Clarke
World
Clarke
Clarke
Clarke
Clarke
World
Clarke

<0.24
26
0.24

900

for coals worldwide [52].


for US coals [51].
reference plant (worldwide averages of all parts of all plants) [16].
for angiospermous plants worldwide [49].
for gymnospermous plants worldwide [49].
for coal ashes worldwide [52].
for US coal ashes recalculated from coal data for 13.1% ash yield [51].
reference plant ash (worldwide averages of all parts of all plants) [16], recalculated from plant data for 4.9% ash yield [1].
for plant ashes [50].

Table 3
Summarised comparisons between the mean values of elements and some properties for biomass and biomass ash and those for coal and coal ash, respectively (based on Tables 1
and 2, and [17,16,4952]).
Biomass compared to coal

Biomass ash compared to coal ash

Higher contents or values of:


 Ag, B, Br, Ca, Cl, H, I, K, Mg, Mn, Na, O, P, Rb, Ru, Zn
 Carbohydrates
 Carbonates
 Chelates
 Chlorides
 Dry water-soluble residue
 Extractives
 Light hydrocarbons
 Moisture
 Organically bound inorganic elements
 Oxalates
 Oxygen-containing functional groups (hydroxyl, carboxyl, ether and ketone
groups) with highly reactive functionalities (COOH, OCH3 and OH)
 Phosphates
 Volatile matter
 Water-soluble components
Lower contents or values of:
 Al, As, Au, Ba, Be, Bi, C, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, F, Fe, Ga, Gd, Ge, Hf, Hg, Ho,
In, Ir, La, Li, Lu, Mo, N, Nb, Nd, Ni, Os, Pb, Pd, Pr, Pt, Rh, S, Sb, Sc, Se, Si, Sm, Sn, Sr,
Ta, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, Zr
 Aromaticity
 Ash yield
 Bulk density
 Fixed C
 Friability
 Functionalities
 Higher heating value
 Hydrocarbons
 Initial ignition temperature
 Inorganic matter
 Peak combustion temperature
 pH
 Oxyhydroxides
 Silicates
 Sulphatessulphides

Higher contents or values of:


 Ag, B, Br, Ca, Cl, Cr, Cu, Ga, Hg, I, K, Mg, Mn, Mo, Na, P, Rb, Sr, Te, Zn
 Dry water-soluble residue
 pH
 Carbonates
 Chlorides
 Oxyhydroxides
 Phosphates
 Water-soluble components

(2) low values of C, xed C (FC), ash yield (A), N, S, Si and initial
ignition and combustion temperatures of biomass, and low contents of many TEs including hazardous ones in biomass and BA
(Tables 13).
3.2.1. Volatile matter, combustion temperatures and reactivity
The high VM content (especially combustible VM) and low initial ignition and combustion temperatures (Table 1 and Fig. 1) are
among the greatest advantages of biomass for thermochemical

Lower contents or values of:


 Al, As, Au, Ba, Be, Bi, Cd, Ce, Co, Cs, Dy, Er, Eu, F, Fe, Gd, Ge, Hf, Ho, In, Ir, La, Li,
Lu, Nb, Nd, Ni, Os, Pb, Pd, Pr, Pt, S, Sb, Sc, Se, Si, Sm, Sn, Ta, Tb, Th, Ti, Tl, Tm, U,
V, W, Y, Yb, Zr
 Ash-fusion temperatures
 Bulk density
 Silicates
 Sulphates-sulphides

conversion because they are criteria for the highly reactive nature
of this fuel [19,53,54]. Biomass volatiles mainly consist of different:
(1) combustible species such as CH4, C2H2, CO, H2, H2S, tars and
other mainly light hydrocarbons; and (2) incombustible components, namely CO2, HCl, H2O, N2, NH3, NOX (NO, NO2), N2O, KCl,
KOH, NaCl, NaOH, SOX (SO2, SO3), others [10,17,28,5459].
Additionally, biomass is enriched in carbohydrates and H instead
of hydrocarbons [60]. For example, biomass has a VM/FC ratio typically >4.0 and frequently exceeding 5.0, while for coal VM/FC ratio

336

S.V. Vassilev et al. / Fuel 158 (2015) 330350

Table 4
Major advantages of biomass and biomass fuels.

















Renewable energy source for natural biomass


CO2 neutral conversion and climate change benets
Transition to low carbon economy, namely from hydrocarbon to carbohydrate and H resources
Use of nonedible biomass
Conservation of fossil fuels
Low contents of ash, C, FC, N, S, Si and most trace elements
High concentrations of volatile matter, Ca, H, Mg and P, structural organic components, extractives, water-soluble nutrient elements
Biodegradable resource with great reactivity and low initial ignition and combustion temperatures during conversion
Huge and cheap resource for production of biofuels, sorbents, fertilizers, liming and neutralizing alkaline agents, building materials, synthesis of some minerals and
recovery of certain elements and compounds
Reduction of biomass residues and wastes
Decrease of hazardous emissions (CH4, CO2, NOX, SOX, toxic trace elements)
Capture and storage of toxic components by ash
Use of oceans, seas, low-quality soils and non-agricultural, degraded and contaminated lands
Restoration of degraded and contaminated lands
Diversication of fuel supply and energy security
Rural revitalization with creation of new jobs and income

Table 5
Major disadvantages of biomass and biomass fuels.






















Incomplete renewable energy resource for biofuels with respect to complete life cycle assessment
Competition with edible biomass (food, feed), bre and biomaterial productions
Damage of natural ecosystems (water, soil, land use changes, deforestation, biodiversity, land degradation, fertilizers, pesticides, contaminants)
Insecurity of biomass feedstock supply
Indenite availability of sustainable biomass resources for production of biofuels and chemicals
Omission of sustainable criteria for production of biomass resources for biofuels and chemicals
Lack of global monitoring and control of biofuels production with certication of origin and source
Miss of accepted terminology, methodologies, standards and classication and certication systems
Insufcient knowledge and variability of composition, properties and quality for assessment and validation
High contents of moisture, water-soluble fraction, Cl, K, Na, O and some trace elements (Ag, Br, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Se, Tl, Zn, others)
Low energy density (bulk density and caloric value)
Low pH and ash-fusion temperatures
Low bulk density and ne size of ash with increased dust inhalation risk
Technological problems during processing (agglomeration, deposit formation, slagging, fouling, corrosion, erosion)
Odour, emission and leaching of hazardous components during disposal and processing
Use of extra water, fertilizers and pesticides
Great growing, harvesting, collection, transportation, storage and pre-treatment costs
Regional and seasonal availability and local energy supply
Limited practical experience in biofuel production and unclear utilisation of waste products
Miss of developed biomass markets
High investment cost

WWB - wood and woody biomass


HAB - herbaceous and agricultural biomass
HAG - herbaceous and agricultural grass
HAS - herbaceous and agricultural straw
HAR - herbaceous and agricultural residue
AB - animal biomass
MB - mixture of biomass
CB - contaminated biomass
AVB - all varieties of biomass
P - peat
L - lignite
S - sub-bituminous coal
B - bituminous coal
A - algae

Fig. 1. Mean proximate composition of the biomass groups and sub-groups, and four solid fossil fuel types based on 87 biomass varieties and 38 solid fossil fuels [1], wt.%.

337

S.V. Vassilev et al. / Fuel 158 (2015) 330350

is virtually always <1.0 [61]. Therefore, the high content of VM


(more typical of wood and woody biomass and herbaceous and
agricultural biomass in Fig. 1 and [1]) causes: (1) low ignition temperature [41,57,62,63]; (2) easier and rapid ignition, devolatilisation and burning [10,62]; (3) higher production of combustible
gas and inorganic vapours [8,41,63]; (4) faster oxidation of VM
than char [53,54] or more aming combustion and less char
combustion [64]; (5) improved combustion resulting in a better
and quicker burnout with lower unburned C in the ash [19,62,65]
when the fuel particle size is suitable; and (6) formation of biochar
with high specic surface area [4,12]. Finally, there is a synergic
benet during co-ring of coal with biomass because the high
VM contents in biomass provide a more stable ame for the mixed
fuel [66]. On the other hand, the combustion of high VM biomass is
rapid and difcult to control, and requires a bigger reactor volume
and optimum design in order to achieve complete combustion and
low pollutant emissions such as CO, unburned products, polycyclic
aromatic hydrocarbons and others [10,64,67].
3.2.2. Carbon, xed carbon and hydrogen
The low values of C (more typical of algae and herbaceous and
agricultural biomass in Fig. 2 and [1]) and FC (more characteristic
of semi-biomass, animal biomass, straws and grasses in Fig. 1
and [1]) have signicant benet for reducing CO2 emissions during
biomass conversion. Carbon dioxide is a primary agent of global
warming among the greenhouse gas emissions despite that CH4
and N2O have 25 and 300 times stronger global warming potential
than CO2, respectively [30]. As a result CO2 constitutes 72% of the
total anthropogenic greenhouse gases, causing between 9% and
26% of the greenhouse effect [68]. Carbon dioxide is a major combustion product from all biomass fuels and its emissions are
regarded as being CO2-neutral with respect to the greenhouse
gas effect and this is considered to be the main environmental benet of biomass combustion [23]. However, the incomplete biomass
combustion can also lead to emissions of unburnt C-based pollutants such as CO, methane, polycyclic aromatic hydrocarbons,
dioxins, furans, tar, soot and other hydrocarbons, and special emission reduction measures are applied [23,69]. It is well known that a
fundamental difference between biofuels and fossil fuels is the
lower amount of C and the higher proportion of O and H in biomass

(Fig. 2). This reduces the energy value of biofuel due to the lower
energy contained in CO and CH bonds than in CC bonds [54].
The typical increased H/C and O/C ratios in biomass imply decreasing aromaticity and increasing role of the oxygen-containing
hydroxyl, carboxyl, ether and ketone functional groups [8]. On
the other hand, FC represents the fraction of fuel which will
undergo heterogeneous combustion reactions [54]. The FC, C and
H contents have a direct positive relationship with the caloric values of biomass as latter are generally higher in terrestrial, perennial, forestry and woody biomass, than in aquatic, annual,
herbaceous and agricultural biomass [2,6973]. Finally, the high
content of H in biomass (more characteristic of animal biomass,
semi-biomass and herbaceous and agricultural residues in Fig. 2
and [1]) is an advantage (see also above) due to: increased role
of combustible H2, H2S, carbohydrates, hydrocarbons and
H-containing functional groups, greater volatility and highly reactive nature of this fuel [8,19,53,54].
3.2.3. Structural organic components
It is well known that dependent upon its structural composition
(cellulose, hemicellulose and lignin), each variety of biomass can
be better suited to specic pre-treatment and conversion processes
[14,47,74,75]. For example, the high contents of cellulose (more
typical of wood stems and herbaceous and agricultural stalks and
bres [2]) and hemicellulose (more characteristic of wood twigs,
leaves and barks, algae and some grasses and grains [2]) in biomass
can be leading features for considering suitable processing technologies due to: (1) increased reactivity, hydrophility, hydrolysis,
oxidation, volatility, crystallinity, sugar and inorganic matter;
and (2) decreased caloric value, aromaticity, density and char
yield ([2] and references therein). On the other hand, the high contents of lignin (more typical of agricultural shells, husks and pits,
and certain wood barks [2]) in biomass can be leading features
for considering suitable processing technologies due to: (1)
increased caloric value, density, hydrophobicity, mechanical
strength, binder properties, char yield, aromaticity, soot formation,
variety of functional groups, as well as greater resistance to natural
degradation, biological digestion and many chemical agents; and
(2) decreased inorganic matter, oxidation, reactivity, volatility
and crystallinity ([2] and references therein). Therefore, the

WWB - wood and woody biomass


HAB - herbaceous and agricultural biomass
HAG - herbaceous and agricultural grass
HAS - herbaceous and agricultural straw
HAR - herbaceous and agricultural residue
AB - animal biomass
MB - mixture of biomass
CB - contaminated biomass
AVB - all varieties of biomass
P - peat
L - lignite
S - sub-bituminous coal
B - bituminous coal
A - algae

Fig. 2. Mean ultimate composition of the biomass groups and sub-groups, and four solid fossil fuel types based on 87 biomass varieties and 38 solid fossil fuels [1], wt.%.

338

S.V. Vassilev et al. / Fuel 158 (2015) 330350

structural composition of biomass varieties among biomass groups


and sub-groups were specied for application purposes into six
different structural types (CHL, CLH, HCL, HLC, LCH,
LHC) based on the contents of cellulose, hemicellulose and lignin
(Fig. 3 and [2]). Finally, the dominant occurrence of specic structural components in biomass can also be an advantage as precursors for the production of high quality biochars with high surface
area and specially tailored active sorption properties [2,4]. For
example, biomass varieties enriched in lignin from LCH, LHC
and HLC structural types and from inorganic low acid K type
can favour the production of such advanced biochars [2].
3.2.4. Extractives
The bulk extractives of biomass consist of various organic and
inorganic components extracted individually or sequentially by
different polar or non-polar solvents, namely water, ethanol, benzene and toluene, and occasionally acetone, dichloromethane,
ethers, heptane, hexane, methanol, methylene chloride, petroleum
spirit and their mixtures [2]. The high content of extractives in biomass (more typical of herbaceous and agricultural bres, grasses
and residues, and algae [2]) is an advantage or strong indicators
for: (1) potential production of biodiesel, bioethanol, biomethanol,
bio-oil and other biofuels and biochemicals; (2) occurrence and
potential recovery and use of lipids, proteins, fats, oils, terpenes,
tannins, resins, sugars, starches, organic acids, inorganic salts and
other organic compounds; (3) increased proportions of watersoluble fraction and extractable inorganic matter, and higher
heating value; and (4) decreased oxidation [2,17,53,57,7680].
3.2.5. Ash yield and inorganic matter
The low ash content of biomass (more typical of wood and
woody biomass and some herbaceous and agricultural biomass
varieties in Fig. 1 and [1]) is more desirable and has a great benet
for higher fuel quality [19,81] due to: (1) increasing heating value
[20]; (2) easier thermochemical and biochemical conversions

[69,82,83]; (3) less fouling, deposition, agglomeration, slagging,


corrosion and erosion problems [28,41,69,82]; (4) decreasing operating costs concerning biomass harvesting, transport and processing, gas-cleaning technologies, as well as ash transport, disposal
and utilisation [3,4,69,82,84]; (5) less fuel contamination by soil,
dirt, rainfall, wind, fertilizers, pesticides and additives during biomass growing, harvesting, transport and processing [1,53,85]; (6)
assessing the best time for biomass harvesting [44,86,87] and
others. It is well known that the biggest technological and environmental challenges that biofuel faces today are mostly related to the
occurrence, proportion, origin and behaviour of inorganic matter in
biomass [27,28]. The inorganic constituents in biomass are normally much less than in solid fossil fuels, excluding aquatic biomass, animal biomass and some varieties from herbaceous,
agricultural and contaminated biomass (Table 1, Fig. 1 and [1,2]).
It should be noted that the ash contents in certain seaweeds,
municipal solid wastes, paper sludge and sewage sludge can even
reach up to 5070% [16,8892]. The inorganic matter in biomass
and BA includes mineral matter, namely mineral species and
poorly crystallized mineraloids from different mineral groups and
classes, as well as amorphous inorganic phases with different origin [2,3]. It is supposed that the genetic inorganic types in biomass
and BA may have a leading importance for technological and environmental problems similar to coal and coal ash [27]. Certain
major associations related to the occurrence, content and origin
of inorganic elements and phases were identied in BA system
and they include: (1) SiAlFeNaTi; (2) CaMgMn; and (3)
KPSCl [14]. These associations were applied for classications
of IM in biomass (Fig. 4) and BAs (Fig. 5) to four types (S, C,
K and CK) and six sub-types (S-HA, S-MA, C-MA,
C-LA, K-MA and K-LA). It was found that these systematic
associations have a key importance, namely their potential application for classication and indicator purposes connected with
innovative and sustainable processing of biomass and BA [47].
For example, the concept of dividing IM into detrital, authigenic

WWB - Wood and woody biomass


WWS - Stems
WWBA - Barks
WWT - Twigs
WWL - Leaves
WWO - Others
HAB - Herbaceous and agricultural biomass
HAG - Grasses
HAS - Straws
HAST - Stalks
HAF - Fibers
HASH - Shells and husks
HAP - Pits
HAR - Other residues
AB - Animal biomass
CB - Contaminated biomass
AVB - All varieties of biomass
NB - Natural biomass

Fig. 3. Mean structural composition of the biomass groups and sub-groups based on 93 biomass varieties [2], wt.%.

S.V. Vassilev et al. / Fuel 158 (2015) 330350

339

WWB - Wood and woody biomass


HAB - Herbaceous and agricultural biomass
HAG - Herbaceous and agricultural grass
HAS - Herbaceous and agricultural straw
HAR - Herbaceous and agricultural residue
AB - Animal biomass
MB - Mixture of biomass
CB - Contaminated biomass
AVB - All varieties of biomass
P - Peat
L - Lignite
S - Sub-bituminous coal
B - Bituminous coal
A - Algae

Fig. 4. Areas of 87 biomass varieties and 38 solid fossil fuels in the chemical classication system of inorganic matter in biomass [2], wt.%.

WWB - Wood and woody biomass


HAB - Herbaceous and agricultural biomass
HAG - Herbaceous and agricultural grass
HAS - Herbaceous and agricultural straw
HAR - Herbaceous and agricultural residue
AB - Animal biomass
MB - Mixture of biomass
CB - Contaminated biomass
AVB - All varieties of biomass
P - Peat
L - Lignite
S - Sub-bituminous coal
B - Bituminous coal
A - Algae

Fig. 5. Areas of 87 biomass varieties and 38 solid fossil fuels in the chemical classication system of biomass ash [1,3,7], wt.%.

and technogenic types of biomass (Fig. 4 and [2]), and original (primary) or newly formed secondary and tertiary types of BA (Fig. 5
and [36]) has both fundamental and applied aspects. The detrital
minerals (silicates and oxyhydroxides) are commonly stable during weathering, less mobile (water-insoluble) and less reactive,
and with high-melting temperatures during biomass processing.
In contrast, the authigenic minerals (opal, oxalates, carbonates,

phosphates, sulphates, chlorides and nitrates) are normally unstable during weathering, highly mobile (water-soluble) and reactive,
and with low decomposition or melting temperatures during biomass processing. Further, the technogenic IM includes various
mineral species with more variable properties and behaviour in
comparison with the natural inorganic constituents. Therefore,
IM types, mineral classes and groups and specic mineral species

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S.V. Vassilev et al. / Fuel 158 (2015) 330350

S type

%
60
50
40
30
20
10
0

C type

%
60
50
40
30
20
10
0
%
60

K type

50
40
30
20
10
0

CK type

%
60
50
40
30
20
10
0

Four types

%
60
50
40
30
20
10
0
Amorphous matter

Oxyhydroxides

Crystalline matter

Phosphates

Carbonates

Sulphates

Silicates

Chlorides

Fig. 6. Mean distribution of amorphous matter, crystalline matter and mineral


classes in biomass ash types based on eight biomass ashes produced at 500, 700,
900, 1100, 1300 and 1500 C [6], wt.%.

are likely to be the major reasons for many problems during biomass processing (similar to coal [2]). For example, the authigenic
minerals can be highly responsible for enhanced leaching behaviour, low-temperature transformations, partitioning behaviour
and emission (or capture) of many volatile elements and hazardous
components, corrosion, agglomeration, deposits formation, slagging, fouling, bed deuidization and composition of residues during biomass processing. The detrital minerals can be important
for enhanced abrasion-erosion (hard and angular quartz, feldspars,

rutile, corundum), formation of some low-temperature eutectics,


partitioning element behaviour and for decreasing combustion
efciency and increasing operating costs for the handling of inert
materials during biomass processing. The technogenic minerals
can also be responsible for many of the above listed problems plus
enhanced pollution by heavy metals, and this is because most
semi-biomass fuels contain high levels of TEs [2]. Organic matter
and authigenic minerals in biomass are intimately mixed with each
other and their physical isolation (in contrast to chemical leaching), namely separation by screening, dense media treatment or
otation can be difcult during biomass upgrading. In contrast,
detrital minerals in biomass occur as physically more easily separable particles similar to coal [2]. The unusually high ash yield
determined in some biomass varieties can be a very strong indicator for contamination of biomass by detrital and technogenic materials [1,2]. Hence, many of the key constraints in the efcient
thermal treatment of biomass may arise mostly from authigenic
minerals. However, such minerals and some inorganic elements
in biomass can also have a catalytic effect on thermochemical conversion. Many inorganic elements in biomass are also bound in OM
and these organically associated elements and their phases react
during the thermal treatment of biomass and appear dominantly
as newly formed IM in residues ([2] and references therein).
Finally, the newly formed secondary and tertiary minerals and
phases in the thermochemical products generated from biomass
(various silicates, oxyhydroxides, carbonates, chlorides, phosphates, sulphates, glass and char) also have specic impacts on
the different technological and environmental problems related
to the sustainable utilisation of biofuels (Figs 57 and [37]).
3.2.6. Water-soluble nutrient elements
The high contents of water-soluble macronutrient and micronutrient elements (B, Ca, Cl, Cu, H, K, Mg, Mn, Mo, N, O, P, S, Zn,
others) in biomass and BA (Tables 1 and 2, Fig. 8 and [7]) are a
big advantage. It was found that biomass and BA contain signicant amounts of water-soluble components of major and minor
elements such as Al, C, Ca, Cl, Fe, K, Mg, Mn, N, Na, P, S, Si and Ti,
plus many TEs (As, Ba, Br, Cd, Co, Cr, Cu, Hg, Li, Mo, Ni, Pb, Sb, Se,
Sr, V, Zn) (Fig. 8, [7] and references therein). For example, the content of water-soluble fractions in biomass and BA are much higher
than in coal and coal ash, respectively (Table 1 and [7,93,94]).
Therefore, the water-soluble fractions play a very important role
for biomass (particularly for algae and some herbaceous and agricultural biomass) and especially for all BAs [7]. Most of the above
mobile elements associate preferably with OM in biomass and
water-soluble minerals and phases in biomass and BA (chlorides,
sulphates, oxides, hydroxides, oxalates, and nitrates plus some carbonates, bicarbonates, phosphates, silicates and amorphous material) [6]. Hence, signicant portions of the above listed
water-soluble nutrient elements in biomass and BA are bioavailable and can be used as fertilizers or for soil improvements supplying plant-growing, nutrient and essential elements for improving
the natural balance in the system. Finally, some valuable
water-soluble elements in biomass and BA are easily recoverable
and can nd another industrial utilisation [4]. However, it should
be stated that the future large-scale biomass and BA application
may create new environmental and technological concerns related
to the fate of some water-soluble phases. For instance, these issues
include potentially serious problems related to: (1) unavailable
nutrients as water insoluble glass, silicates, phosphates and char;
(2) hazardous TEs in/on mobile inorganic phases; (3) polluted char
with polychlorinated dioxins and furans, and polycyclic aromatic
hydrocarbons; (4) groundwater contamination; (5) pH shock and
chemical burning damage to plants; (6) disturbing the microorganisms; (7) extra salinity problems; (8) dust emissions; (9) ash swelling and obstructing soil pores ([4,6] and references therein).

S.V. Vassilev et al. / Fuel 158 (2015) 330350

341

Fig. 7. Positions of eight biomass varieties in the phasemineral classication of biomass ash, based on mean contents of amorphous matter, silicates and others
(carbonates + oxyhydroxides + phosphates + sulphates + chlorides) for biomass ashes produced at 500, 700, 900, 1100, 1300 and 1500 C [6], wt.%. Abbreviations: BC, beech
wood chips; CC, corn cobs; MM, marine macroalgae; PP, plum pits; RH, rice husks; SG, switchgrass; SS, sunower shells; WS, walnut shells.

Additionally, the extra accumulation of P, N, K and other plant


nutrients into water is a natural aging process known as eutrophication. This anthropogenic process is a serious problem resulting
in accumulation of large concentrations of specic plant nutrients
in a relatively short amount of time [95].
3.2.7. Alkaline-earth elements
The high contents of alkaline-earth elements (Ca, Mg) in biomass and BA (Tables 1 and 2 and Figs. 4 and 5) are a big advantage
for: (1) soil amendment and fertilization; (2) production of construction materials, adsorbents and ceramics; (3) synthesis of minerals; (4) recovery of valuable components; (5) multicomponent
utilisation; and (6) reduction of some technological and environmental problems ([4] and references therein). Numerous biomass
fuels especially among wood and woody biomass, algae,
semi-biomass, animal biomass and some perennial herbaceous
and agricultural biomass, are normally enriched in these elements
([1] and Figs 4 and 5). Proportions of alkaline-earth elements in
biomass occur in mobile (water-soluble) and bioavailable Ca- and
Mg-bearing chlorides, sulphates, oxalates and nitrates plus some
carbonates and phosphates, as well as amorphous material with
both organic and inorganic character [2]. These organic and
inorganic CaMg-containing phases in biomass form active and
semi-active newly formed CaMg minerals and phases in BA
such as limeportlandite, periclasebrucite, anhydritebassanite
gypsum, feldspars and other silicates, glass, carbonates, phosphates
and chlorides. These reactive substances in water cause hardening
and binder effects in the system during evaporation of water. Such
effects are a result of formation of new and relatively more stable
silicates, sulphates, carbonates, hydrates and oxyhydroxides
containing water molecules and/or hydroxyl groups during hydrationdehydration, hydroxylationdehydroxylation and subsequent
carbonation processes of BA. These newly formed crystalline and
amorphous products bind the pozzolanic (glass) and inert phases

(inactive to less active quartz, cristobalite, tridymite, mullite, other


silicates and some char) relatively quickly in such multicomponent
systems [6]. The above-mentioned complex processes play a leading role in the production of construction materials and some other
applications, and the bulk chemical and phasemineral composition of BAs provides vital information for that purpose. Therefore,
it is possible to classify BAs to phasemineral types and
sub-types with dominant pozzolanic, inert or active properties
(Fig. 7 and [4,6]) for different innovative and sustainable utilisation
of BAs, as well as reducing some technological and environmental
problems related to BA [4,6]. For example, biomass fuels with
higher Ca contents exhibit more manageable slagging, fouling
and corrosion problems [96,97]. The higher Ca contents in some
biomass (mostly woody biomass) can reduce the lime/calcite usage
and plant operation costs of the installed ue gas desulphurisation
systems during the acid gas abatement ([2,4] and references
therein). Additionally, some biomass fuels highly enriched in Ca
and Mg could produce suitable bed materials that may reduce
the need to use additives in uidized-bed combustion chambers
[4]. This type of combustion requires additional use of quartz,
other silicates or carbonates as a bed material. Hence, biomass
highly enriched in Ca and Mg (wood biomass and animal biomass)
and silica (straws, grasses and rice husks) may reduce such a need
[2]. Finally, the reason for increased capture of some volatile hazardous air pollutant elements in BAs is caused mostly by some
Ca- and Mg-bearing minerals or phases with well-known sorbent
properties, which are present in the combustion residues such as
carbonates, oxyhydroxides, phosphates, sulphates, chlorides and
amorphous matter [4,6]. The increased capture and immobilisation
of some volatile and hazardous elements (C, S, Cl and in particular
TEs) in combustion residues is phenomenon and it is known as the
concept of self-cleaning fuels ([2,4,6] and references therein).
Additionally, the data [24,6] also indicate that the biomass energy
can be not only carbon-neutral, but also with some extra

342

S.V. Vassilev et al. / Fuel 158 (2015) 330350

Fig. 8. Mean and range contents of water-soluble elements leached from: (a) biomass; and (b) biomass ash [6], wt.%.

carbon-capture and storage potential due to xation and immobilisation of CO2 in the combustion residues. For example, the mineral
composition of BAs clearly shows the intensive formation of various newly formed carbonates. These carbonates are a result of
solidgas reaction between the volatile CO2 (released from biomass or occurring naturally in the atmosphere) and Ca and Mg
oxyhydroxides formed during biomass combustion [24,6]. The
last phenomenon is actual extra CO2 capture and storage mechanisms. Hence, there are potential possibilities for reduction of
harmful emissions by modication of the feed fuel composition
through tailored and self-cleaning fuel mixtures during co-ring
or co-gasication of biomass with fossil fuels [2,3]. Finally, various
CaMg minerals in BA like Ca silicate hydrate gel, Ca aluminosilicate hydrate, portlandite, calcite and ettringite can be formed in
the ash disposals (under high pH) and such crystallisations may
reduce mobility either by physically reducing the porosity of the
ash or by chemically binding the elements ([4] and references
therein). On the other hand, the high contents of alkaline-earth
and alkaline oxides in ash may cause burning damage on human
and plant tissues [98].
3.2.8. Nitrogen
The low N content in biomass (especially for wood and woody
biomass in Fig. 2 and [1]) is a big advantage due to decreased
NOX and ammonia (HN3) emissions, acid precipitation, ozone

pollution, photochemical smog and corrosion problems during


thermochemical conversion [23,54,71,72,99,100]. Therefore, the
concentration of N (together with S, Cl, some trace elements, plus
dioxins and furans) in biomass and/or BA needs to be regulated
within fairly stringent limits to maintain an acceptable feedstock
quality [23,44,69]. On the other hand, the high N concentration is
characteristic of certain biomass (semi-biomass, animal biomass,
algae, others) and it is also an indication for some eutrophication
and use of N-bearing fertilizers, additives in semi-biomass or substances in the pelletisation process [1,23,72,95,101]. The NOx
emissions may decrease by: (1) application of low N fuels; (2)
emission reduction techniques such as staged combustion and
injection of NH3 or urea [10]; and (3) coal and biomass blending
because biomass produces NO destroying species such as ammonia
and hydrocarbon radicals in the furnace [102].
3.2.9. Sulphur
The low S content in biomass (particularly for wood and woody
biomass in Fig. 2 and [1]) is favourable for: (1) lower SOx
emissions, smoke type smog, acid precipitation; and (2) limited
generation of ne particulates, less stable and mobile sulphates,
deposit formation, agglomeration, slagging and corrosion; during
thermochemical conversion [37,23,54]. The low S concentration
is also an indication of decreased contamination of biomass by
additives, fertilizers, pesticides, adhesives, glues, lacquer, dyestuff

S.V. Vassilev et al. / Fuel 158 (2015) 330350

or preservatives [72] which are typical for semi-biomass and agricultural biomass residues. On the other hand, the S contents can be
high in some biomass varieties (semi-biomass, animal biomass and
certain herbaceous and agricultural biomass [1]) and can cause
problems regarding SOX emissions, generation of ne particles,
deposit formation and corrosion [23,69,72]. However, the alkaline
and alkaline-earth compounds in biomass and BA are effective capture agents of S in newly formed sulphates during thermochemical
conversion of biomass [5,6].
3.2.10. Silicon
The low Si and silicate contents (especially for wood and woody
biomass, animal biomass and algae in Figs 4 and 5, and [1]) in biomass and BA is an advantage for less erosionabrasion and slagging
problems during processing of biomass and BA. For example, high
contents of hard (harder than the steels and refractory materials),
coarser-grained and angular mineral particles of silica minerals
(quartz, cristobalite, tridymite), feldspars and other silicates plus
glass, rutile and corundum identied in biomass and BA can be a
reason for increased wear of the metal equipment surfaces [4].
Additionally, the low Si contents are an advantage for a limited formation of low-temperature alkaline silicates and glass, as well as
ne and respirable crystalline silica minerals (especially cristobalite) in BA that can present slagging and health risks ([4] and references therein).
3.2.11. Trace elements
The low contents of many TEs including hazardous ones in biomass and BA (Table 2 and [7]) are favourable for less environmental problems related to the emissions of such elements and
formation of dangerous components during biomass conversion
(see above). On the other hand, the high concentrations and modes
of occurrence of some TEs (Ag, Au, B, Be, Cd, Cr, Cu, Mn, Ni, Se, Zn,
others) may have a resource recovery potential for certain biomass
varieties and BAs and an economical assessment is required in such
cases [4,7]. For example, it was found that some ashes enriched in P
(from sewage sludge, meat-bone meal, olive residue, poultry litter
and peach pits) or Cu and other trace elements (from municipal
solid waste and sewage sludge) are very perspective for that purpose [103105]. However, this topic is still at initial stage of investigations [7].
3.2.12. pH
The high pH of BA (Table 1) is favourable for soil amendment
and fertilization due to the alkaline character (liming effect) that
promotes: (1) base cations; (2) acid neutralizing potential; (3)
higher salinity (electrical conductivity); (4) mineral weathering
(dissolution of aluminosilicates, clay dispersion and illuviation);
(5) lower acidic leaching of hazardous elements from soil into
water stream resulting in their less mobilisation and bioavailability; (6) reduced Al, Mn and Fe plant toxicity by decreasing the
exchangeable contents of these ions in acidic soils; (7) enhanced
biological activities and better environment to some microorganisms; and (8) improved texture, aeration and water holding capacity ([4] and references therein). It is well known that the alkaline
environments suppress the release of a large number of elements
(Al, Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb, Sn, Ti, Zn among others); however, such conditions enhance release of oxyanionic-forming species of As, B, Cr, F, Mo, Sb, Se, V and W ([4,7] and references
therein). Unfortunately, prolonged leaching during BA weathering
in disposal sites could provoke a decrease of pH and signicant
release of many TEs from BA ([4,7] and references therein). In contrast, the low pH values of biomass are a disadvantage because the
solubility of most elements is markedly pH sensitive and most elements are much more mobile under acidic than alkaline conditions
([4,7] and references therein). The pH values of water leachates for

343

biomass are slightly acidic to neutral with salty to brine total mineralisation (Table 1 and [2]) and variable electrical conductivity [2].
As a result, different elements in biomass tend to be mobile (see
above) and they are prone to pose environmental concerns [7].
3.3. Disadvantages of biomass
The major disadvantages related to the use of biomass as fuel
are listed in Table 5. Most of the common barriers related to environmental, technological, economic and social issues have been
described relatively well, while the obstacles connected with the
composition and properties of biomass and biofuel have been discussed to a lesser extent in the literature [148]. Some of the major
disadvantages related to the composition and properties of biomass and/or BA include: (1) high values of moisture (M) and O in
biomass, water-soluble fraction, alkaline and halogen elements,
and some hazardous TEs in biomass and BA; (2) low values of
energy density (bulk density and caloric value), pH and
ash-fusion temperatures (AFTs) of biomass, and bulk density and
size of BA; (3) highly variable composition and properties of biomass and BA (Tables 13); and (4) indenite availability of sustainable biomass resources for production of biofuels and chemicals.
3.3.1. Moisture
The high moisture content in biomass is one of the major disadvantages. This content normally varies in the interval of 363%
(Table 1) and it can even reach up to 91% [16]. In contrast, the moisture occurrence in peat and coal is commonly in the more narrow
range up to 20% [1]. Moisture in biomass is a mineralised aqueous
solution containing various cations, anions or non-charged species
[2]. The high M content has numerous negative effects such as: (1)
problems during biofuel pre-treatment, preparation and upgrading
(drying, grinding, separation, baling, pelletization, briquetting, torrefaction, others); (2) complications during biomass conversion
(excluding liquefaction, gasication, alcoholic fermentation and
anaerobic digestion), namely lowering caloric value and grinding
capacity (non-friable properties), poor ignition, reducing the combustion temperature and combustion efciency, longer residence
time in combustion units, ame stability problems, delaying the
release of volatiles, forming a large quantity of ue gas and fumes,
incomplete cracking of the hydrocarbons, increasing unburned C
levels in ash, and larger equipment dimensions; (3) precipitation
of chlorides, carbonates, sulphates, nitrates and phosphates during
biomass drying; (4) enhanced leaching (Ca, Cl, K, Mg, Na, P, S, TEs)
during biomass storage and processing; and (5) deterioration of
biofuel due to the microbial activity and promoting health risk
resulted from fungus and moulds proliferation in biomass [1,10,1
4,18,19,28,39,53,54,56,64,79,83,106108]. It is well known that
the raw biomass with >3050% moisture content does not burn
before the partial evaporation of some moisture [83]. On the other
hand, when the fuel is air-dried the stored moisture equilibrates
with the ambient relative humidity and this equilibrium (saturation point in air-dried fuel) is normally 2030% for woody biomass
[19,57,109] and 610% for other biomass fuels [110].
3.3.2. Alkaline and halogen elements
The high contents of alkaline and halogen elements such as K,
Na, Cl and occasionally Br, Cs, F, I, Li and Rb (Tables 1 and 2, and
[7]) with unfavourable modes of occurrences (organic matter, chlorides, sulphates, carbonates, oxalates, nitrates, oxyhydroxides,
phosphates, amorphous material, others), are among the major
technological and environmental challenges of biomass conversion
because they cause: (1) increased volatilization and formation of
many dangerous components (Cl2, HCl, HBr, HF, dioxins, furans,
TEs, others); (2) enhanced ne particulate emissions; (3) greater
quantity of water-soluble fraction; (4) generation of low-melting

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S.V. Vassilev et al. / Fuel 158 (2015) 330350

eutectic phases and low ash-fusion temperatures; (5) higher


amount of active melts with low viscosity; (6) increased deposit
formation, fouling, agglomeration, slagging and corrosion; (7)
enhanced deleterious effects on the cement-based construction
materials incorporating BA; (8) greater deterioration rates and
accelerated deactivation of catalysts used for selective catalytic
reduction of NOX and SOX; (9) fouling of the solid oxide fuel cells
anodes in gasiers; and (10) burning damage on human and plant
tissues by alkaline oxides in BA ([27] and references therein).
Numerous biomass fuels among agricultural and herbaceous biomass, annual plants, algae, semi-biomass, animal biomass and
wood branches and leaves are normally enriched in alkaline and
halogen elements (Figs 25, and [1]). The technological countermeasures include fuel selection and blending, fuel pre-treatment
(mostly water washing) and application of appropriate additives,
temperature and ash cleaning systems. For example, biomass harvested and left in the eld for a prolonged period of time (natural
rain washing) or industrial biomass washing to remove
water-soluble phases prior to use of biomass fuels may reduce
some technological and environmental problems. However, such
future large-scale leaching may create new environmental
concerns related to the fate of water-soluble Cl-, K-, Mg-, N-, Na-,
P- and S-bearing phases and different hazardous and mobile TEs
associated with them (Fig. 8 and [17] and references therein).
Additionally, the highly variable phase and chemical composition
of biomass fuels gives the possibility of reducing high contents of
alkaline and halogen elements and improving the fuel performance
by modication of the feedstock composition through tailored fuel
mixtures ([6] and see below). On the other hand, the high contents
of alkaline and halogen elements can have some positive effects
during biomass conversion. For example, some alkaline inorganic
constituents of biomass (like KCl, NaCl and others) can act as catalysts or catalyst precursors for thermochemical conversion of biomass [111113]. In some cases, the high alkali and Cl contents in
biomass lead to the enhanced formation of KCl and NaCl in ash
and this can lower the level of gaseous Cl available for the synthesis of dioxins and furans [23]. Moreover, the alkaline BAs have been
used for neutralization of wastes, as a source for production of
potash, liming and tannin neutralizing agents, fertilizers, glass,
glaze, soap, detergents, composites, synthesis of minerals and
other applications [4,114116]. Finally, some Br and Cl enriched
biofuels could also play the role of self-cleaning fuels for the successful capture and immobilisation of Hg ([46] and references
therein). The use of such advanced approaches is of particular
interest because the improved and/or cleaner fuel blends may contribute for reducing or avoiding many technological or environmental problems during biomass thermochemical conversion.

3.3.3. Hazardous trace elements


The high contents of some toxic and potentially toxic TEs such as
Ag, Be, Cd, Cl, Cr, Cu, Hg, Mn, Ni, Se, Zn, others in biomass and/or BA
(Table 2 and [7]), and especially those with unfavourable modes of
occurrences, are among the most serious disadvantages during biomass conversion. It was recently revealed that the greatest ecological challenges related to some TEs in biomass and BA include their:
(1) high concentrations; (2) unfavourable modes of occurrence
(organic matter, carbonates, chlorides, sulphates, oxalates, nitrates,
oxyhydroxides, phosphates, amorphous material, others); (3)
enhanced volatilization and limited retention and capture performance during biomass combustion; and (4) increased leaching
behaviour during biomass and BA processing or storage [7]. It is
well known that TE contaminants can be accumulated in biomass
fuel throughout air, water, soil, pesticides, fertilizers and additives
([7] and references therein). It was found that the thermochemical
conversion of biomass can increase the negative TE impacts
because signicant amounts of TEs (As, Cd, Cr, Cu, Hg, Ni, Pb, V
and Zn) that have been mobilised from geochemically stable
sources are remobilised during biomass conversion [101]. For
instance, TEs such as As, Br, Cd, Cr, Hg, Pb, Sb, Se, V and Zn demonstrate the highest volatilization potential during biomass combustion, whereas TEs such as As, Ba, Br, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo,
Ni, Pb, Sb, Se, Sr, V and Zn show signicant water-soluble occurrence in biomass and BA (Figs 8 and 9, and [4,7] and references
therein). Additionally, the above TEs tend to occur in much more
mobile and hazardous compounds than in coal and coal ash because
they associate preferably with the easily decomposed OM and
water-soluble minerals and phases in biomass and BA ([4,6,7] and
references therein). These modes of element occurrence favour
their high mobility (leaching and volatilization) during biomass
and BA processing. Hence, some dangerous, volatilized and
water-soluble elements might cause some environmental pollution
of the air, water (surface and subsoil water), soil, ora and fauna
with possible subsequent penetration into the food chain during
biomass and BA utilisation [4]. Further, the observations that most
of the hazardous TEs tend to have higher water leaching potential
from BA than from biomass give important information for the sustainable utilisation of BA, especially for soil application and recovery of elements [6]. For example, it was found that lter y ashes
and ashes from semi-biomass should be avoided for soil application
because they are commonly highly contaminated with hazardous
TEs such as As, B, Ba, Cd, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Se, Zn and others
([4] and references therein). Therefore, the concentration of hazardous TEs (plus Cl, N and S) in biomass and BA needs to be regulated within fairly stringent limits to maintain an acceptable
quality [7,10,16,23,44,69,72,117119] and highly efcient

Fig. 9. Mean and range contents of elements volatilized from biomass during combustion [6], wt.%.

S.V. Vassilev et al. / Fuel 158 (2015) 330350

separation of these elements in biomass power plants is required


[28,82]. On the other hand, the highly variable phase and chemical
composition of biomass fuels gives the possibility of reducing the
harmful emissions by modication of the feed fuel composition
through tailored fuel mixtures ([6] and see above). For instance,
some biofuels can be to some extent self-cleaning fuels because
a number of their original constituents and their newly formed

345

minerals and phases are active during thermochemical conversion


and can play more or less a capture and immobilisation role for
the volatile hazardous elements. This is due to the enrichment of
biomass in: (1) active alkaline-earth and alkaline constituents that
form carbonates, oxyhydroxides, phosphates, sulphates, chlorides
and amorphous matter; and (2) structural organic components that
can produce unburned chars with high specic surface area [6].

Fig. 10. Mean ash-fusion temperatures for the biomass groups and sub-groups, and three solid fossil fuel types based on 90 biomass varieties and 37 solid fossil fuels in
increasing order of the uid temperatures [6], C. Abbreviations: A, aquatic biomass; AVB, all varieties of biomass; B, bituminous coal; C, coal; CB, contaminated biomass; DT,
initial deformation temperature; FT, uid temperature; HAB, herbaceous and agricultural biomass; HAF, herbaceous and agricultural bres; HAG, herbaceous and agricultural
grasses and owers; HAH, herbaceous and agricultural husks; HAPT, herbaceous and agricultural pits; HAR, other herbaceous and agricultural residues; HAS, herbaceous and
agricultural straws; HASH, herbaceous and agricultural shells; HAST, herbaceous and agricultural stalks; HT, hemispherical temperature; L, lignite; NB, natural biomass; S,
sub-bituminous coal; ST, spherical temperature; WWB, wood and woody biomass; WWBA, wood and woody barks; WWL, wood and woody leaves; WWO, other wood and
woody biomass; WWR, wood and woody roots; WWS, wood and woody stems; WWST, wood and woody stumps; WWT, wood and woody twigs.

Fig. 11. Areas of low (<1200 C), medium (12001400 C) and high (>1400 C) hemispherical (HT) ash-fusion temperatures for 60 biomass varieties in the chemical
classication system of biomass ash [6], wt.%.

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S.V. Vassilev et al. / Fuel 158 (2015) 330350

3.3.4. Ash-fusion temperatures


The low ash-fusion temperatures of biomass are a serious disadvantage. It was found that AFTs of biomass are more variable
than those of coal, but they are normally lower, excluding certain
lignites and biomass varieties from S and C ash types (Figs
10 and 11, and [3,6]). It is widely accepted that most of the severe
deposit formation, slagging and fouling problems during biomass
thermochemical conversion result from the low ash-melting temperatures [4,6]. Some indicative trends of natural biomass in comparison with coal were identied recently [2], namely the potential
of biomass to have normally:
(1) Higher values of Ca, Cl, K, Mg, Mn, Na, P, carbonates, chlorides, phosphates, organically bound inorganic elements
and water-soluble components.
(2) Lower values of Al, Fe, N, S, Si, Ti, inorganic matter, oxyhydroxides, silicates and sulphatessulphides.
Hence, such differences are reasons for the lower AFTs of biomass in comparison with coal. For instance, it was found that the
high concentrations of K-, Si-, P-, S-, Fe-, Na- and Mg-containing
minerals (excluding the highly enriched in Si biomass varieties)
and low contents of Ca-, Al- and Ti-bearing minerals are commonly
responsible for decreased AFTs of biomass (Fig. 12 and [6]). The
low ash-fusion biomass varieties normally have high slagging
propensity due to formation of low-temperature melts and their
subsequent intensive melt crystallization followed by abrupt glass
generation during cooling at relatively low temperatures [6]. The
lower AFTs with short softening-melting range and high
ow-dissolution rate (S-MA inorganic sub-type) seem to be the
worst case for slagging and fouling (Fig. 11 and [6]). A selection
of optimal temperatures for thermochemical conversion is
required to avoid the above problems. Another possibility is the
preliminary biomass washing to eliminate the water-soluble components which contribute greatly for lower AFTs [97,120123].
Additionally, a benecial approach for problematic low
ash-fusion biofuels or alternative bed materials for uidized bed
combustion is to use various additives, namely kaolinite, mullite,
clinochlore, bentonite, K feldspar, plagioclase, olivine, quartz, lime,
bauxite, gibbsite, diaspore, corundum, hematite, calcite, dolomite,
magnesite, ankerite, sand, high alumina sand, limestone, diatomaceous earth, dicalcium phosphate, chalk, elemental S, peat, coal and
coal ash ([6] and references therein). The application of such additives is to prevent the agglomeration, sintering and slagging tendencies by achieving higher ash-melting temperatures. The
purpose of the above blending is to provoke the intensive formation of more refractory minerals (silica minerals, mullite, and Ca
and Mg silicates, oxides and phosphates) and less uxing phases
(K and Na silicates, chlorides, sulphates and phosphates) in the system [6]. However, there are many solid fuels which are naturally
abundant in these refractory minerals and appropriate blending
of such fuels can avoid the use of expensive biomass
pre-treatment procedures and non-fuel additives [6]. For example,
the favourable or less problematic future fuel mixtures between
biomass, coal and other solid fuels may include an adjustment of
chemical and phase composition for fuel blends to t preferentially
some chemical sub-types of BA (Fig. 11 and [6]). Hence, the fuel
mix can play a leading role to solve different technological and ecological problems (see also above).
3.3.5. Oxygen
Biomass is highly oxygenated fuel due to the carbohydrate
structure with respect to conventional fossil fuels with hydrocarbon structure [97]. The high O content in biomass (especially
among agricultural and herbaceous biomass, wood and woody biomass and algae in Fig. 2 and [1]) is a disadvantage because of: (1)

%
60

<1200oC
mean 1101oC

1200-1400oC
mean 1284oC

>1400oC
mean 1520oC

50

CaO

40
30

SiO2

20
10
0
1000

K2O
1100

1200

1300

1400

1500

1600

%
8
7

Al2O3

MgO
5
4

P 2 O5

3
2
1000

1100

1200

1300

1400

1500

1600

%
4.5
4
3.5
3
2.5
2

SO3
Fe2O3

1.5

Na2O

TiO2

0.5
0
1000

1100

1200

1300

1400

1500

1600
o

Hemispherical (HT) ash fusion temperature, C


Fig. 12. Mean contents (wt.%) of the chemical components and mean hemispherical
(HT) ash-fusion temperatures (1101, 1284 and 1520 C) for three temperature
ranges (<1200, 12001400 and >1400 C) based on 60 biomass varieties [6].

reduced energy value [54]; (2) less predictable behaviour of highly


oxygen-functionalized carbohydrates [60,124]; and (3) greater
volatility [54], inorganic vapours [8], smoking [40] and soot formation [45] during thermochemical conversion. On the other hand,
biomass has high reactivity as a result of signicant concentrations
of O in highly reactive forms such as COOH, OCH3 and OH functional groups [61].
3.3.6. Energy density, bulk density and caloric value
The low energy density (both low bulk density and heating
value) of biomass is a signicant disadvantage for biomass conversion (Table 1). For example, the energy density of biomass is only

S.V. Vassilev et al. / Fuel 158 (2015) 330350

1040% of that of most fossil fuels [35,57] and biomass heating values generally are slightly over half that of coal [18]. Furthermore,
the biomass particle densities are about half that of coal, whereas
the biomass bulk densities are about one fth that of coal [18]. The
lower energy density of biomass requires a biomass resource close
to the processing facility, high storage cost and minimal storage
time because the weathering and bacteria can lower the energy
quality of the biomass [13]. Additionally, the low bulk densities
of biomass particles are prone to adhesion by the build-up of static
electric charge [125]. Therefore, different pre-treatment procedures such as drying, baling, chopping, milling, screening, pelletisation, briquetting, torrefaction and others are applied to: (1)
increase the energy density; (2) depress the self-ignition; and (3)
improve the storage, resistance, grindability, hydrophobicity, biological degradation, strength, transportation, feeding and conversion of biomass. The torrefaction process is an advanced
approach for that purpose [40]; however, the application of such
low-temperature pyrolysis technology seems to be much more
economically perspective to generate high-value products such
as biochar (for soil amenders, fertilizers and C sequestration),
adsorbents, activated carbons, catalyst supporters, metal reductants, biocarbon electrodes, additives in polymer/rubber composites and others [4,109,126] than to produce a simple and cheap
solid biofuel just for combustion and gasication. On the other
hand, the low particle densities help biomass particles to oxidize
at rates much higher than coal [18].
3.3.7. Size
The ne size and low values of bulk density of BA (Table 1) are a
disadvantage. For example, biomass y ashes are light materials
having bulk density mostly between 101 and 830 kg/m3 (mean
392 kg/m3), while the same value for coal ashes is much higher,
namely 4001100 kg/m3 (mean 800 kg/m3) ([4] and references
therein). The size of biomass y ash particles varies from 10 to
50 nm to more than 12 mm, but these powder materials are commonly very ne as their median size is dominantly below 10
100 lm [4]. Therefore, biomass y ashes tend to be lighter and
ner than coal y ashes and these characteristics increase health
and safety risks during transport, storage and processing of biomass y ashes due to particulate emissions and possible dust
inhalation as the smallest particles are of the greatest concern
due to their composition ([4] and references therein). This situation can be improved by y ash compaction into pellets, briquettes
and agglomerates or during storage.
3.3.8. Variable composition and properties
The highly variable composition and properties of biomass and
BA (Tables 1 and 2, and Figs 17) are serious barrier issues for the
application of specic and suitable thermochemical and biochemical conversion technologies of biomass and utilisation of BA. These
disadvantages include: (1) irregular quality; (2) possible interrupted processing; (3) less predictable behaviour of biofuels and
their products; and (4) challenges to meet the technical and environmental requirements. On the other hand, this variation is an
advantage for application of more diverse biomass conversion technologies, as well as more variable BA utilisation directions such as
soil amendment and fertilization, production of different materials
(construction materials, adsorbents, ceramics, synthesis of minerals), recovery of valuable components (char, water-soluble, cenosphereplerosphere, magnetic and heavy fractions; and elements)
and multicomponent utilisation [4]. Finally, the denitive utilisation, technological and environmental advantages and challenges
related to biomass and BA associate preferentially with specic
organic and inorganic types or sub-types (Figs. 37, 11 and 12)
and they can be predictable by using the combined chemical and
phasemineral classication approaches [17].

347

3.3.9. Sustainable biomass resources


It was highlighted that the utilisation of biomass resources will
be one of the most important factors for environmental protection
in the 21st century [25]; however, it is well known that under current policies, the environmental effects from biofuel production
might be worse than those from fossil fuels [127]. Therefore,
one of the biggest challenges for large-scale production of biofuels
and biochemicals is the availability of sustainable biomass
resources for such purposes. Natural biomass is a renewable
energy source, while biofuel is still an incomplete renewable
energy resource at present [1]. Unfortunately, the modern bioenergy chains are usually associated with additional use of fossil fuels
during growing, fertilizing, harvesting, transportation, storage,
pre-treatment and conversion of biomass, as well as discharge
and handling of wastes, emissions and other environmental
impacts, when considering the complete biomass life cycle assessment [23,29,30,101]. Furthermore, the biofuel demands should not
compete with food and feed production.
The conversion of biomass sources from natural ecosystems
(forests, tundra, grasslands, prairies, pastures, peatlands, wetlands,
rivers, lakes, seas and oceans) into energy resources may lead to
serious environmental problems related to balance, regeneration,
biodiversity, biocoenosis and life cycle assimilation in such systems [2]. Shortly, not enough knowledge is available to truly comprehend the importance of the natural ecosystems and given this
lack of knowledge humans should be very careful not to further
disturb and destroy these native systems. The natural ecosystems
are relatively equilibrium habitats (despite the global and regional
pollutions) and they should be avoided, to a maximum extent, as
resources for biofuel or chemical production. There is balance in
composition, modes of occurrence and behaviour of mobile elements (mostly nutrients) in biomass communities, species and
plant parts when considering the biomass regeneration in natural
ecosystems. For example, the sustainable forest management
by clearing, thinning or trimming, and selective harvesting with
removal of trees, shrubs, branches, twigs and foliage (alive or dead)
can reduce signicantly the nutrient capital and balance of the forest ecosystem because large amounts of the most mobile nutrients
can be exported. It was emphasized that with increasing out-take
of the most nutrient-rich parts of the trees as fuel, measures must
be taken to ensure that the nutrient balance of the forest biotope is
maintained and recycling of wood ash will thus be an important
part of a sustainable forestry ecosystem [128,129]. However, the
subsequent sustainable use of BAs as bioavailable nutrients back
to the forest soil cannot solve the potential balance problem
because these ashes have totally different phase composition,
modes of nutrient and trace elements occurrence, properties and
behaviour in comparison with the original biomass and associated
soils [4]. Similar assumptions can also be valid for the other natural
ecosystems. Therefore, the large-scale use of such unfavourable
biomass resources will cause further disturbances and imbalances
in the already stressed natural ecosystems and similar opinions
have already been highlighted [30,127]. These observations lead
to the conclusion that exploitation of natural ecosystems should
remain undisturbed to a maximum extent in order to avoid
adverse impacts. In the current trend towards large-scale production of fuel and energy from biomass resources it would thus be
desirable to restrict the exploitation of natural ecosystems and
instead derive the biomass from a limited number of feedstocks.
The above reasons strongly indicate that the potential favourable
biomass resources for biofuel production, despite some possible
technological and contamination problems, should be focused (in
decreasing order of signicance) preferably on terrestrial and
aquatic phytomass, zoomass and excreta such as:
(1) Non-edible agricultural, forest, feed and food residues.

348

S.V. Vassilev et al. / Fuel 158 (2015) 330350

(2) Semi-biomass (contaminated biomass and industrial biomass wastes).


(3) Short-rotation energy crops such as specically cultivated
forest, grass and algae plantations, but grown only on existing low productive, degraded or contaminated non-arable
land and in wastewater or contaminated ponds.
(4) Animal and human wastes.
Thus, the potential biomass resources for biofuel and biochemical production should always be divided initially into sustainable and unsustainable management resources under strictly
specied environmental criteria. For example, the complete biomass life cycle assessment is very important tool for that purpose [23,27,29,30,43,48,101,130]. Additionally, the remote
sensing methods and geographical information systems (satellite,
aerial and ground-based remote sensing) have recently become
critically important approaches for the environmental impacts,
land-use change, site-specic management, production, estimation, monitoring, planning, control and policy implementations
of sustainable biomass feedstock [131133]. Subsequently, when
there is conrmation of sustainable origin and/or production of
biomass feedstock only after that biofuels can be assigned correctly to the currently used terms such as primary and secondary biofuels, biofuel generations (IIV) and biofuel types
(solid fuel, diesel, alcohols, syngas, hydrogen, chemicals, others)
commonly used in practice. It is noted that this might
very-well reduce the overall available and sustainable biomass
resource due to insecurity of biomass feedstock supply.
Therefore, it may be speculated that the huge contribution of
biomass in the future energy mix is signicantly overestimated
if appropriate additional measures and corrections are not taken
into considerations regarding the availability and management of
unsustainable and unfavourable biomass resources for production of biofuels. Still, biomass could play an important role as
a fuel and energy resource when combined with other efforts,
namely other types of renewable energy and overall reducing
the fuel and energy consumption.
4. Conclusions
Certain conclusions about the advantages and disadvantages of
biomass composition and properties for biofuel application based
on parallel and detail investigations of numerous characteristics
for both biomass and coal and their conversion products can be
made:
(1) Some of the major advantages related to the composition
and properties of biomass and/or BA include: (1) high values
of volatile matter, H, structural organic components, extractives and reactivity of biomass, water-soluble nutrient elements and alkaline-earth elements in biomass and BA, and
pH of BA; and (2) low values of C, xed C, ash yield, N, S,
Si and initial ignition and combustion temperatures of biomass, and low contents of many trace elements including
hazardous ones in biomass and BA.
(2) Some of the major disadvantages connected with the composition and properties of biomass and/or BA comprise:(1)
high values of moisture and O in biomass, water-soluble
fraction, alkaline and halogen elements, and some hazardous trace elements in biomass and BA; (2) low values
of energy density (bulk density and caloric value), pH
and ash-fusion temperatures of biomass, and bulk density
and size of BA; (3) highly variable composition and properties of biomass and BA; and (4) indenite availability of
sustainable biomass resources for production of biofuels
and chemicals.

(3) The conversion of biomass sources from natural ecosystems


into energy resources may lead to serious environmental
problems. The native ecosystems should be avoided, to a
maximum extent, as resources for biofuel production. The
potential favourable resources for that purpose should be
focused preferably on: (1) non-edible agricultural, forest,
feed and food residues; (2) semi-biomass (contaminated
biomass and industrial biomass wastes); (3) short-rotation
energy crops such as specically cultivated forest,
grass and algae plantations, but grown only on existing
low productive, degraded or contaminated non-arable land
and in wastewater or contaminated ponds; and (4)
animal and human wastes. The potential biomass resources
for biofuel and biochemical production should always be
divided initially into sustainable and unsustainable management resources under strictly specied environmental
criteria.
(4) It was found that the disadvantages of biomass for biofuel
and biochemical applications prevail over the advantages;
however, the major environmental, economic and social
benets appear to compensate the technological and other
barriers caused by the unfavourable composition and properties of biomass.

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