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Fuel
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Review article
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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
331
332
332
332
333
335
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%
332
[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].
333
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
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.
334
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
gymnospermous plantse
World reference
plant ashh
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
a
b
c
d
e
f
g
h
i
Element
Clarke for
coalsa,b
World reference
plantc
Clarke for
gymnospermous plantse
World reference
plant ashh
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
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
(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
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
Table 4
Major advantages of biomass and biomass fuels.
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
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
(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
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
Fig. 3. Mean structural composition of the biomass groups and sub-groups based on 93 biomass varieties [2], wt.%.
339
Fig. 4. Areas of 87 biomass varieties and 38 solid fossil fuels in the chemical classication system of inorganic matter in biomass [2], wt.%.
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
340
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
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,
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.
342
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
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
344
Fig. 9. Mean and range contents of elements volatilized from biomass during combustion [6], wt.%.
345
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.%.
346
%
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
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
348
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