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Fuel 181 (2016) 133

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Fuel
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Review article

Composition, properties and challenges of algae biomass for biofuel


application: An overview
Stanislav V. Vassilev , Christina G. Vassileva
Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, Block 107, Sofia 1113, Bulgaria

h i g h l i g h t s
 Composition and properties of algae and algae ash were summarized.
 Comparative characterization between algae and other solid fuels was given.
 Advantages of algae composition and properties were described.
 Disadvantages and challenges of algae composition and properties were discussed.

a r t i c l e

i n f o

Article history:
Received 22 March 2016
Received in revised form 21 April 2016
Accepted 21 April 2016
Available online 28 April 2016
Keywords:
Algae
Algae ash
Composition and properties
Advantages
Disadvantages

a b s t r a c t
Algae-based fuels are considered to be the most sustainable, renewable, effective and environment
friendly response to climate change and foodfeed security, as well as the only renewable energy
resource that has the capacity to meet the global demand for fuels in the long-term. Therefore, an
extended overview of the composition, properties and challenges of algae biomass for biofuel application
was conducted based on reference peer-reviewed data plus own investigations. Initially, some general
considerations such as current bioenergy situation and significance of biofuel generations, as well as different aspects related to biomass use as biofuels are discussed. Then, common issues concerning taxonomical classification, habitat environment, carbon reserve capacity, production, use, and main
advantages and disadvantages of algae or algae biofuel are addressed. Further, more than 135 characteristics related to the chemical, phase and mineral composition and properties of algae and algae ash are
evaluated and compared to those of terrestrial biomass, coal and their ashes. As a result specific benefits
and obstacles connected with the composition and properties of algae and algae ash are discussed. The
behaviour of organic and inorganic matter during algae combustion is also described. Finally, the major
technological and environmental challenges related to algae-based fuels are emphasized. The present
data demonstrate that the high contents of inorganic matter with unfavourable modes of element occurrences (chlorides, sulphates, carbonates, oxalates, nitrates and some oxyhydroxides, phosphates and
amorphous material) in algae and algae ash provoke the most critical technological and environmental
challenges during algae processing for biofuel application and especially during algae thermochemical
conversion. Another very important challenge addressed is the indefinite availability of sustainable algae
resources for production of biofuels and biochemicals and certain recommendations are given. It was
found that the disadvantages of algae biofuel application prevail significantly over the advantages; however, the major economic, environmental and social benefits appear to compensate the technological and
other barriers caused by the unfavourable composition and properties of algae.
2016 Elsevier Ltd. All rights reserved.

Contents
1.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.
General considerations about biomass and biofuel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.
Common issues concerning algae and algae biofuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

Corresponding author.
E-mail address: vassilev_stan@yahoo.com (S.V. Vassilev).
http://dx.doi.org/10.1016/j.fuel.2016.04.106
0016-2361/ 2016 Elsevier Ltd. All rights reserved.

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Nomenclature
AA
AFT
BA
daf
db
DTA
DWR
FC
GHG
HHV
HTA

2.
3.

4.

algae ash
ash-fusion temperature
biomass ash
dry, ash-free basis
dry basis
differential-thermal analysis
dry water-soluble residue
fixed carbon
green house gasses
higher heating value
high-temperature ash (>500 C)

MM
ppm
SEM
TE
TGA
VM
XRD
%

marine macroalgae (sea lettuce)


part per million
scanning electron microscopy
trace element
thermo-gravimetric analysis
volatile matter
X-ray powder diffraction
weight %

1.2.1.
Taxonomical classification and habitat environment of algae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.2.
Carbon reserve capacity of algae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.3.
Algae production and use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.4.
Advantages of algae and algae biofuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.5.
Disadvantages of algae and algae biofuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.6.
Composition and properties of algae. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Materials, methods and data used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.
General considerations about composition and properties of algae and algae ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2.
Common trends about the composition and properties of algae and algae ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3.
Chemical composition and properties of algae and algae ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.3.1.
Moisture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.3.2.
Ash yield and inorganic matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3.3.
Volatile matter, reactivity and initial ignition and combustion temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3.4.
Bulk density, calorific value and energy density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3.5.
Elemental composition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.3.6.
Water-soluble fraction, extractives, pH and electrical conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.3.7.
Ash-fusion temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.4.
Phase and mineral composition of algae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.4.1.
Organic matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.4.2.
Inorganic matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.5.
Phase and mineral composition of algae ash. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.5.1.
Inorganic amorphous matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.5.2.
Silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.5.3.
Oxides and hydroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.5.4.
Sulphates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.5.5.
Carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.5.6.
Chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.6.
Behaviour of algae during combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.7.
Major technological and environmental challenges related to algae-based fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

1. Introduction
1.1. General considerations about biomass and biofuel
Biomass as a renewable source can be converted into solid, liquid and gaseous biofuels for generating bioenergy, as well as into
some chemicals. Bioenergy has been recognised as an important
component in many futures energy scenarios and could contribute
significantly to economic, social and environmental goals [1,2]. For
example, biomass currently contributes about 815% of the world
energy supplies as heat, electricity and fuels for transportation and
up to 3350% of the worlds current primary energy consumption
could be met by biomass by 2050 ([3] and references therein).
Additionally, the substitution of fossil fuels by biofuels appears to
be an effective strategy to meet not only the future world energy
demands but also the requirement for reducing greenhouse gasses
(GHG) and particularly carbon emissions originating mostly from

fossil fuels combustion [2]. Therefore, the focus on bioenergy as


an alternative to fossil energy has increased tremendously in
recent times because of global warming problems.
In total about 9597% of the worlds bioenergy is currently
produced by direct combustion of biomass. The perspective of
increasing large-scale combustion of natural biomass and its cocombustion with 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 solid fossil fuels (coal, peat, petroleum coke) seems to
be one of the main drivers for biofuel promotion in many countries
worldwide in the near future ([3] and references therein). Biofuels
are more environment friendly than fossil fuels [4,5]; however,
important potential constraint for global biofuel expansion is the
ongoing debate on criteria for sustainable production, energy balances and GHG savings of biofuels [2]. For instance, terrestrial
bioenergy production systems are now facing issues related to food

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

security, indirect C emission, carbon debt from land clearance and


land use changes, and they are becoming a sustainability hurdle for
further expansion [2,4,6,7]. Thus, sustainable biofuels that reduce
GHG emissions and protect ecosystems are likely to require nonagricultural feedstocks, such as wastes and residues, integration
with food production, lignocellulosic materials and algae, as well
as plants grown on low-quality land [1].
Extensive investigations have been carried out worldwide
recently to enhance biomass use instead of fossil fuels for energy
production ([3,814] and references therein). For that purpose
numerous biomass varieties among biomass groups, namely wood
and woody biomass, herbaceous and agricultural biomass, aquatic
biomass (including algae sub-group), animal and human biomass
wastes, semi-biomass and their biomass mixtures can be used
for biofuels and biochemicals [8,9,14]. Solid (biomass), liquid
(bioethanol, biobutanol, bio-oil and biodiesel) or gaseous (biogas,
biomethane, syngas, biohydrogen) biofuels obtained from drying,
densification, anaerobic digestion, fermentation, extraction, transesterification, torrefaction, pyrolysis, gasification, liquefaction or
genetically modified organisms can be categorized into 1st, 2nd,
3rd and 4th biofuel generations according to the origin of the biomasses used [2,46,1523].
The first-generation biofuels are produced from edible feedstock based mainly on sugar, starch, grains, seeds and oils (sugarcane, corn, sugar beet, sunflower, rapeseed, wheat, barley, oil palm,
soybean, animal fat, potato, others). These biofuels originated from
food and feed crops cannot meet the demand because they are
unsustainable, inefficient and inadequate to argument rising
requirements [2,17,21]. For example, their use is claimed to be
not very successful and raised controversial debates due to the
food versus fuel dilemma because they affects global security,
prices and markets of food [4,6,23,24]. Therefore, a gradual shift
towards the second generation biofuel sources, which offer greater
potentials, is necessity [2].
The second-generation biofuels are produced from non-edible
crops based mostly on lignocellulosic feedstock derived from forest
and agriculture residues and industrial organic wastes such as
wood, forest residues, demolition wood, straw, grass, municipal
solid waste, refuse-derived fuel, and sewage sludge. These biofuels
bring many more advantages compared to the first-generation
ones because they do not compete with food and feed supplies
and normally have higher yield and lower land requirements
[4,17]. However, the limitations of the first- and secondgeneration biofuel resources show clearly that they are grossly
inadequate to meet global demands for biofuels due to concerns
over protection of global ecosystems, land availability and competing land use and land use changes in a sustainable and climatefriendly way [2,19]. Additionally, one of major drawbacks for the
second-generation biofuels is the lack of efficient technologies for
commercial applications [4].
The third-generation biofuels are produced from algae biomass
as feedstock [2,4,5,17,20,23,25]. Algae have received great attention
as novel resource to produce biofuels and/or biochemicals [23]. The
third-generation biofuels are seen as a technically viable alternative
energy approach that may overcome the major drawbacks associated with the first- and second-generation biofuels [4]. However,
the positive aspects of algae-based fuel production in terms of the
economic, environmental and social aspects have not been sufficient at present to produce algae on a large commercial scale due
to the high production costs [2,21,2628]. Despite the above limitations, it was emphasized that algae biofuel production will become
competitive in the medium term if considered along with technologies and production of higher value co-products such as biofertilizers, biopolymers and other bioproducts [2].
The fourth-generation biofuels are based on microscopic organisms produced from genetically modified microbes, yeast, fungi,

microalgae and cyanobacteria that convert CO2 directly to fuel or


modifying the oil-storing capabilities of organisms [19,20,29]. Artificial photosynthesis could also be involved to produce such genetically reengineered biofuels [29].
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 utilization of biomass. 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 [8]; (2) organic and inorganic phase composition of biomass [9]; (3) phase-mineral and chemical composition of
biomass ash (BA) [3]; (4) potential utilization, technological and
ecological advantages and challenges of BA [10]; (5) behaviour of
biomass during combustion, namely phase-mineral transformations of organic and inorganic matter [11], as well as ash-fusion
and ash-formation mechanisms of biomass types [12]; and (6)
advantages and disadvantages of biomass composition and properties for biofuel application [14]. New chemical and mineralogical
classifications of biomass or BA have been introduced therein
[3,812,14]. Additional investigations on trace element concentrations and associations in biomass and BA have also been conducted
[13]. It was highlighted in the above studies that the aquatic biomass group and especially the algae sub-group have rather distinct
composition and properties in comparison with terrestrial biomass
and solid fossil fuels, and such differences have very important
ecological and technological impacts during utilization of algae
and their conversion products.
1.2. Common issues concerning algae and algae biofuel
Numerous studies connected with the characterization and
application of algae have been performed worldwide ([123,25
61] among others) and some common issues concerning algae
and their use as biofuels and biochemicals are summarized below.
1.2.1. Taxonomical classification and habitat environment of algae
Algae are diverse group of photosynthetic organisms ranging
from unicellular (microalgae or phytoplankton) to multicellular
(macroalgae or filamentous) living in both marine and freshwater
environments [16,21,23,25]. These simple chlorophyll containing
organisms are able to photosynthetically convert sunlight, water
and CO2 to a wide range of metabolites and chemicals in algal biomass [16,21,23]. There are about 55 000 species and more than
100 000 strains of marine, brackish, fresh water and terrestrial
algae [2,20]; however, only a dozen of algae species are commercially cultivated worldwide [56]. Algae are categorized mostly into
several main classes or broad groups based on their photosynthetic
pigmentation variations, namely green, blue-green, red, brown and
golden algae [16,22,37].
The pigment, growth rate, size, weight and chemical composition of algae are significantly affected by their habitat environment
conditions such as light, temperature, pH, salinity, nutrient, pollution, and even water motion, particularly depending on their taxonomical classes and species [23,56]. Among the conditions, light is
the most principal contributor. Thus, the classes of macroalgae are
vertically distributed from the upper zone (close to the sea surface)
to the lower sublittoral zone because algae have their respective
pigments, which absorb selectively the light with specific wavelengths [56]. Certain algae can tolerate and adapt to a wide variety
of environmental conditions and they can be produced all year
round [23].
Macroalgae are comparatively large, multicellular and photoauxotrophic organisms [21,23] and belong to the lower plants,
consisting of a leaf-like thallus instead of roots, stems and leaves

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

[56]. They are able to grow up to 60 m in length [25]. Macroalgae


are classified mainly into three major groups according to the thallus colour derived from photosynthetic pigmentation variations,
namely green (Chlorophyta), red (Rhodophyta) and brown
(Phaeophyta) [16,22,25,56].
Microalgae are one of the most primitive forms of plants. They
are unicellular or simple-multicellular photosynthetic microorganisms and have size of <400 lm and normally of 130 lm in diameter [2,16,21,23,25,27,28]. It is estimated that 50 000 species of
microalgae exist; however, only few were used practically [21].
Biologists have categorized microalgae in a variety of classes,
mainly distinguished by their pigmentation, life cycle and basic
cellular structure [16]. The most important classes or categories
of microalgae in terms of their abundance are: (1) diatoms (Bacillariophyceae); (2) green (Chlorophyceae); (3) blue and blue-green
cyanobacteria (Cyanophyceae); (4) golden (Chrysophyceae); and
(5) red (Rhodophyceae) algae [16,18,21,23,25,27,28,46]. Diatoms
are the dominant life form in phytoplankton and probably represent the largest group of biomass producers on Earth [16,18].
Cyanobacteria are referred to as blue-green microalgae even
though they combine characteristics of bacteria and algae
[16,18,28,29]. Microalgae can be grouped additionally into photosynthetic, non-photosynthetic, autotrophic, heterotrophic, mixotrophic, prokaryotic and eukaryotic [21,23,46]. The algae groups
also include various single-celled creatures that are simple collections of cells, without differentiated tissues [37]. Besides to natural
environments, microalgae can be cultivated in freshwater, seawater and waste water within open ponds (raceway) and closed
photo-bioreactors [23].
1.2.2. Carbon reserve capacity of algae
Billions of years ago the atmosphere was filled with CO2 and
thus there was no life on Earth. Life on Earth started with

cyanobacteria and algae and these humble photosynthetic organisms sucked the atmospheric CO2 and started releasing extra oxygen. As a result, the levels of CO2 started decreasing to such an
extent that life evolved on Earth. Once again these smallest organisms are poised to save us from the threat of global warming [16].
Most anthropogenic emissions of CO2 resulted from fossil fuels
combustion as two sectors, electricity and heat generation and
transport, produced nearly two-thirds of these global emissions
at present [2,25]. It is well known that algae are more photosynthetically efficient and have higher productivity rates than terrestrial plants and as a consequence algae have greater capacity to
generate and store carbon resources because they are more efficient CO2 fixers [15,23,25,56]. For example, microalgae are able
to mitigate CO2 from 10 to 50 times higher than terrestrial plants
[25]. Producing 1 t of algal biomass fixes 1.62.0 t of CO2 because
approximately half of the dry weight of algal biomass is C
[15,16,21,25,28,58]. Thus, algae have a huge potential to considerably contribute to GHG emission reductions right at the very first
stage of the feedstock production [28].
1.2.3. Algae production and use
The total annual world production of algae biomass is about
12 million t dry basis (around 16 million t wet basis) for macroalgae, and about 9200 t dry basis for microalgae, which were harvested from wild habitats and aquaculture farms [22,23,56]. The
amount of the mass-cultivated macroalgae has continuously
increased over the last 10 years at an average of 10% [56]. About
98% of commercial algae biomass production is currently with
open ponds because this cultivation seems to be the most economical and preferable way [23]. Heterotrophic microalgae are more
flexible than autotrophic microalgae for the cultivation because
they can grow under light free condition and been found capable
of accumulating higher lipid in the cells [21]. Algae have very high

Table 1
Commercial applications of algae.
Product

Use

Agar

Food ingredient, hydrocolloids, fruit preserves, clarifying brewing agent, paper industry and other pharmaceutical and
biological/microbiological uses
Food additive, textile printing, pharmaceutical, medical, paper, cosmetic and fertilizer industries
Preservatives in food, pharmaceutical, cosmetic and chemical industries
Food supplement as antioxidant and food dye additive
Supplement for vitamin C and precursor for vitamin A, food additive as antioxidant and colouring agent
Aviation gas, biobutanol, biodiesel, bioethanol, biogas, biohydrogen, biomethane, biooil, biosyngas, gasoline, jet fuel,
solid fuel
Various biofuels and chemicals
Combustion, agricultural and sorbent uses
Ion exchange materials that bind strongly heavy metal ions
Gels, food additive, pet food, toothpaste
See beta-carotene
Catalytic properties due to alkali and alkaline earth species
Medicinal and industrial uses
Chemical, cosmetic and farming industries
Skin foods as thickening agents, water-binding agents and antioxidants
Compost and/or vermicompost
Phytocolloids such as agar, carrageenan and alginate. Food industry
Gasoline, biodiesel, jet fuel, renewable hydrocarbons, alcohols, biogas

Alginate
Antioxidants
Astaxanthin
Beta-carotene
Bioenergy and biofuels
Biorefinery products
Biochar
Biosorbents
Carragen or carrageenan
Carotenoids
Catalysts
Chemicals
Conditioners
Cosmetic products
Digester residue
Extraction of hydrocolloids or gums
Extraction of lipids, carbohydrates, starch
and cellulose
Extraction of minerals and trace elements
Extraction of proteins
Feed
Fertilizers
Food and drink
Fruit and vegetable preservatives
Glass production
Paper pulp supplements
Pharmaceutical applications
Phytosterol
Pigments
Textile production
Therapeutic materials

Food supplements, metallurgy, glass production


Animal/fish feeds, fertilizers, industrial enzymes, bioplastics, surfactants
Animal food
N-, P- and K-rich fertilizers
Nori, aonori, kombu, wakame, jam, cheese, wine, tea, soup, noodles, pasta, beverages, powders, tablets, capsules, others
Food industry
Glass industry
Paper industry
Pharmaceutical industry
Food supplements
Natural colourants in paper and textile industries
Textile industry
Pharmaceutical industry

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Table 2
Major advantages of algae and algae fuels.
Sustainable, renewable, effective and environment friendly biofuel that can meet the global energy demand
Transition to low carbon economy, namely from hydrocarbon to carbohydrate, protein and lipid resources
Huge and superior feedstock to displace terrestrial biomass for producing bioenergy
Enormous greenhouse gas uptake and especially superior CO2 capture and sequestration with extra oxygen release while growing
Mostly nonedible and non-toxic resources
No competition or lower risk of competition with feeds and foods
Diversification of fuel supply and energy security
Conservation of fossil fuels
Mitigate negative effects of spiking crude oil prices and reduce the dependency on foreign oil imports
Rural revitalization and bring social benefits with creation of new jobs and income
High energy conversion efficiency by photosynthesis
High productivity with rapid growth rate and high growing yield
Easily cultured and readily and rapidly bioengineered
No herbicide or pesticide is recommended during cultivation
Easy adaptability nature in wide range of climatic conditions
Grow almost anywhere. Do not need agriculturally productive or environmentally sensitive land and can grow even in industrial, municipal and agricultural waste
waters, contaminated ponds and on wastelands
Use of oceans, seas, ponds and low productive, degraded and contaminated non-arable lands
Prevent eutrophication and pollution in aquatic ecosystems
Restoration of degraded and contaminated areas and ponds
Huge and relatively cheap resource for production of biochemicals, sorbents, fertilizers, building materials, synthesis of some minerals and recovery of certain elements
and compounds
Highly biodegradable resource with quick bioremediation
Reduction of algae residues and wastes
Great reactivity and low initial ignition and combustion temperatures during conversion
Decrease of some hazardous emissions (CO2, SOX, NOX, toxic trace elements) by capture and storage of toxic components in ash
Low values of C and some trace elements
High values of volatile matter, Au, B, Br, Ca, I, Mg, P, Ti, structural organic components, extractives, carbohydrates, proteins, lipids, water-soluble nutrient elements

Table 3
Major disadvantages of algae and algae fuels.
Incomplete renewable energy resource for biofuels with respect to complete life cycle assessment
Indefinite availability of sustainable algae resources and miss of sustainable criteria for biofuel production
Utilization of fossil fuels during algae processing
Insecurity of algae feedstock supply, regional and seasonal availability and local energy supply
Lack of global monitoring and control of algae fuel production with certification of origin and source
Miss of developed algae and biofuel markets and regionally constrained market structures
High production costs for growing, harvesting, collection, transportation, storage and pre-treatment and low cost efficiency with high initial capital investment
The only biofuel production approach is not commercially viable
Miss of established transparent policy frameworks and instruments (subsidies, mandates and tax credit incentives)
Possible competition with edible algae and biomaterials production
Potential environmental problems due to acidification and contamination of waters with consequent large-scale eutrophication and eco-toxicity during algae
cultivation
Damage of natural ecosystems (water, soil, biodiversity conservation, eutrophication, contaminants)
Disturbance of the ecosystem balance in the already stressed lakes, ponds, seas and oceans
Harmful algal blooms in global waters
Utilization of arable land or land use changes
Odour, potential dangerous emissions (Cl, CH4, CO2, SOX, NOX, toxic trace elements), ozone layer depletion and leaching of hazardous components during disposal and
processing
Unclear utilization of waste products
Health problems due to neurotoxic properties of some algae
Use of genetically modified organisms in algae cultivation and in production of biofuels
Technological problems during algae production and use (miss of technological infrastructures and well managed practices, complications with the algae cultivation
and harvesting)
High use of nutrient-rich water or fertilisers are occasionally required for algae cultivation
Use of extra water during algae processing
Limited practical experience in biofuel production
Technological problems during thermo-chemical processing (separation, agglomeration, deposit formation, slagging, fouling, corrosion, erosion)
Direct combustion and gasification of algae is restricted due to ash chemistry
Miss of accepted terminology, methodologies, standards and classification and certification systems
Insufficient knowledge and variability of composition, properties and quality for assessment and validation
High contents of ash, moisture, water-soluble fraction, Cl, K, N, Na, O, S, Si and many trace elements (Ag, As, Cd, Co, Cr, F, Ga, Pb, Se, Sn, Sr, Th, Zn, others) including
hazardous ones
Low contents of H and organic matter
Low energy density (bulk density and calorific value)
Low ash-fusion temperatures
Low bulk density and fine size of ash with increased dust inhalation risk

productivities when cultivated on nutrient-rich (with N and P)


wastewaters such as municipal effluents, domestic sewage, dairy
manure effluents and source-separated urine [6,15,43]. Phytoplankton chlorophyll a concentration is the most widely used for

identification of algae biomass on a weight or volume basis, in


the form of photosynthesis performance index [20].
Algae deliver the highest lipid amount among all biofuels
feedstocks available on the market nowadays [28] and their

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

triglyceride production rates are normally 45220 times higher


than terrestrial biomass [27]. For example, oil yields per hectare
(on an annual basis) from certain algae strains can be much higher
than from corn (300 times), soybean (100130 times), jatropha (30
times), rapeseed (1020 times), oil palm (10 times), other traditional oil plants (10100 times) and terrestrial crops (731 times)
[2,15,16,18,28]. As a result about 47 000308 000 l of oil per hectare could be produced annually using algae [16]. While a terrestrial crop cycle may take from three months to three years for
production, algae can start producing oil within 35 days and
thereafter oil can be harvested on daily basis [18]. It was estimated
that the algal biodiesel is close to the exergy of the common diesel
fuel and gasoline [54]. Finally, the potential bioethanol production
can be 23 400 kg ha 1 year 1 for macroalgae [4].
Algae have numerous commercial applications (Table 1) in
energy, agriculture, chemical, pharmaceutical, food, textile,
cosmetic, glass, paper and other industries [2,4,5,7,1518,
2123,25,28,36,40,44,51,53,56].
1.2.4. Advantages of algae and algae biofuel
The advantages and disadvantages of algae for biofuel applications and production of biochemicals have been discussed in
numerous investigations [2,47,1418,2023,2529,34,37,39,44,4
5,47,4951,53,54,56] and they are listed in Tables 2 and 3. It was
summarized that algae-based fuels are considered to be the most
sustainable, renewable, effective and environment friendly
response to climate change and food security, as well as the only
renewable energy resource that has the capacity to meet the global
demand for fuels in the long-term [2,7,18,21,28,50]. For example,
algae have proven to be a superior and huge feedstock to fully
and partly displace terrestrial biomass for producing sustainable
bioenergy and biomaterials [5,7,21,23,27,28,56].
Numerous advantages (Table 2) are attributed to algae-based
biofuels and biochemicals and some of the most important ones
are shortly described below. It should be noted that the benefits
in some cases can be barriers in other circumstances and vice versa
during algae application.
Algae grow almost anywhere in both fresh and saline water and
they do not need agriculturally productive or environmentally sensitive land or require much less land for their cultivation than terrestrial crops [2,4,15,17,18,21,25,56]. Additionally, algae have easy
adaptability nature for surviving in wide range of climatic conditions [21] and they grow even in industrial, municipal and agricultural waste waters and on wastelands [2,4,6,18,21,23,28,51].
Algae have rapid growth rate with high growing yield per hectare as their productivity is higher than that of the terrestrial biomass [2,4,5,15,17,18,2023,2528,34,37,44,61]. It is well known
that algae are the fastest growing organisms in the world and they
only take hours to reproduce [2]. For example, they grow 2030
times quicker than food crops holding up to 30 times more fuel
than proportionate measures of other biofuel sources [2]. The net
annual harvest of algal biomass yields 4100 t dry biomass per
hectare per annum [2,15,20,22,34,53]. Microalgae have higher
yield per hectare than macroalgae [22]. For instance, microalgae
have a harvesting cycle of 110 days, which allows for several harvests in a very short time frame [23,28]. Given the right conditions,
microalgae can double its volume or mass overnight [2,21,25] as
some microalgal strains are capable of doubling their mass even
within hours (about 3.5 h) [6,21,23,25,26]. As a result, microalgae
could be produced at productivity rates about 500 kg in a
1000 m2 pond for a single day [27].
Algae have high energy conversion efficiency by photosynthesis
[22,27,29,44,56]. For example, they convert solar energy into
chemical energy with much higher photosynthetic efficiency
(48% and up to 10% for some microalgae) than that of terrestrial
biomass (0.52.2%) [22,25,27,29,44,56]. Furthermore, algae

processing normally require less energy than the algae provide


[2,18].
Algae have lower risk or no competition with foods and feeds
[4,18,21,28,56]. Therefore, algae-based fuels can provide a buffer
for mitigating the food/feed vs. fuel problem in the long-term
[18,28]. For example, it was found that algal feedstock is not
impacted by food market price volatilities as is the case for other
bio-based fuels, which ensures higher price stability of the algaebased fuel for the consumers [28]. Additionally, algae-based fuels
could mitigate negative effects of spiking crude oil prices (and subsequently gasoline prices) and further reduce the dependency on
foreign oil imports [28].
Algae prevent eutrophication and pollution in water ecosystems
[23,45,58]. For instance, in eutrophic sea areas, seaweed cultivation has the excellent effect of decreasing eutrophication and to
reduce the risk of red tide occurrence and to help for nutrient control and ocean remediation [45]. Furthermore, algae depollute the
waters by absorbing the urea expelled animals and at the same
time increases the CO2 conversion into biomass [18].
Algae have greenhouse gas uptake and especially CO2 capture
and sequestration permanently with superior CO2 fixation capacity
and release extra oxygen while growing [2,4,5,1618,21,23,25].
Allied to this is the enormous capacity of the algae to convert
CO2 into biomass, liberating via photosynthesis more oxygen for
the atmosphere even than forests [18].
Algae are non-toxic fuel resource [2,4] and highly biodegradable
[2,4] with quick bioremediation [21]. Additionally, they are easily
cultured and more readily and rapidly bioengineered than other
biomass [37] and no herbicide or pesticide is recommended in
algal cultivation [4,21]. Furthermore, algae are very energy and
oil dense and their fuels can be cost effective with more effort
[2]. Finally, algae-based fuels can bring social benefits with creation of new jobs [28].
1.2.5. Disadvantages of algae and algae biofuel
Various disadvantages (Table 3) are attributed to algae-based
biofuels and biochemicals and some of the most important ones
are shortly described below.
The major obstacle militating against the widespread utilization
of algae is their high production costs and low cost efficiency
because the cultivation, harvesting, separation and processing of
the final algae-based fuels are costly [2,21,2628,58]. For instance,
the production cost of microalgae is about 57 times higher than
for lignocellulosic biomass [27]. Additionally, the production of
algae-based fuels requires high initial capital investment [23,26].
Finally, it was also emphasized that the only biofuel production
approach for algae will not be commercially viable and the economics of other options will play the key role [7,58].
The precise quantity of algae that can be grown, harvested and
processed in a sustainable manner appears unclear [2,6]. For example, the utilization of fossil fuels for cultivation, collection, production, transportation and distribution of algae biofuels is common
[6,58].
Many technological problems related to the production and use
of algae occur. For instance, the absence of technological infrastructures and well managed practices of the algae-based fuels is
a weakness [4,6,28]. Additionally, the ash chemistry restricts the
use of algae for direct combustion and gasification [44]. Complications with the algae cultivation methods are also common [23].
Some limitations for large-scale using of macroalgae for biofuels
production occur as compared to microalgae due to a more complex structure, slower growth rate and lower oil content [28]. However, microalgae harvesting is more difficult than macroalgae [22].
Extensive use of nutrient-rich water or fertilisers (rich in C, N, P,
K and occasionally Si) is commonly required for algae cultivation
[4,6,15,23,26,27,58]. For example, the giant kelp cultivation in

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

the oceans need special equipments such as plastic lines and floating grid of pipes with pumped nutrient-rich deep-ocean water
from 300 m depths plus harvest ships [15,26].
Another serious problem related to algae can be acidification
and contamination of waters with consequent large-scale eutrophication and eco-toxicity [6,39,53,58]. Accumulation of nutrients
into water is a natural aging process; however, anthropogenic
eutrophication is a serious problem resulting in accumulation of
large concentrations of specific plant nutrients in a relatively short
amount of time [39]. This eutrophication has promoted growths of
annual filamentous algae in coastal areas worldwide [53]. When
anthropogenic eutrophication occurs, algae present within the
water reproduce excessively under aerobic metabolism; effectively
using large quantities of the waters dissolved oxygen [39]. This
algal material slowly decomposes and the available oxygen is consumed, resulting in large anoxic areas, where macroscopic animal
and plant species cannot survive [53]. Other possible environmental and health problems can also occur because some algae produce
toxins and are neurotoxic, and may cause serious harm to human
health and aquatic life [28,47,58]. For instance, the Taihu Lake in
China that provides drinking water became a toxic nightmare
because of cyanobacteria bloom [47]. The occurrence of harmful
algal blooms is increasing rapidly in global waters in recent decades [47] and the environmental monitoring will play an important role and will be an on-going requirement [58].
Other possible disadvantages of algae-based fuels can occasionally be: competition with food and fibre products due to increase of
their price or decline of their exports [4,6,49]; utilization of arable
land or land use changes [4,6,58]; negative impact on biodiversity
conservation [4,6,28]; disturbance of the ecosystem balance in the
already stressed lakes, ponds, seas and oceans [15,28,47]; ozone
layer depletion [6]; regionally constrained market structures
[4,6]; use of genetically modified organisms in algae cultivation
and in production of biofuels that can result in their spread in natural habitats, biodiversity loss and human mutations [6,58].
Finally, the miss of established transparent policy frameworks
and instruments such as subsidies, mandates and tax credit incentives do not stimulate the algae-based fuel production [6,28].

1.2.6. Composition and properties of algae


Numerous studies connected with the composition and properties of algae have also been performed worldwide and substantial
data for different algae varieties and their solid products generated
by thermochemical (combustion, pyrolysis, gasification and liquefaction) and biochemical (anaerobic digestion, alcoholic fermentation, aerobic biodegradation) conversions have been collected [1
23,2561]. The solid products generated from algae conversion
mostly include different organic and inorganic residues such as
chars, ashes and slags. Incomplete comparative characterizations
between biomass, algae and other fossil fuels have also been given
in some of the above investigations. However, parallel and detail
comparisons between biomass, algae 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, char and other
organic components) and inorganic matter (mineral classes, groups
and species, and inorganic phases); and (3) various properties
(volatile matter, fixed C, moisture, ash yield, ash-fusion and combustion temperatures, density, pH, calorific value and watersoluble components); are still missing or limited. Therefore, an
attempt to summarize the above important characteristics (more
than 135) based on own studies and reference data from numerous
combined investigations for biomass, algae and coal was undertaken and is described below.

The major aims of the present overview are: (1) to systematize


and summarize the peer-reviewed data; (2) to supply additional
own results; (3) to describe certain basic findings; and (4) to clarify
the advantages and disadvantages related to the algae composition
and properties compared to terrestrial biomass and coal as a traditional fossil fuel. Some potential technological and environmental
challenges during algae processing, as well as application of their
products are also focused.
2. Materials, methods and data used
The summarized data for the composition and properties of biomass, algae and coal based on own results and data-base comprising numerous mostly peer-reviewed publications (totally more
than 870 references) have been used for the present and former
overviews [3,812,14]. Eight biomass samples (beech wood chips,
corn cobs, marine macroalgae, plum pits, rice husks, switchgrass,
sunflower shells and walnut shells) were also collected and studied
in detail for the determination and elucidation of many characteristics related to the chemical and phase-mineral composition of
biomass and BA, and behaviour of biomass during combustion
[3,914]. The samples investigated belong to different biomass
groups and sub-groups classified by origin (biodiversity and
source), as well as to variable organic and inorganic types and
sub-types specified for biomass and BA [3,8,9,12]. 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 (500, 700, 900, 1100, 1300 and 1500 C) and other
procedures described earlier [3,9,1114]. The summarized reference data for algae and the additional detail results for one of
the above biomass samples, namely marine macroalgae (sea lettuce, Ulva lactuca), were used in the present study to demonstrate
the rather different composition and properties of the aquatic biomass group (the algae sub-group) compared to the terrestrial biomass and coal. This sea lettuce is one of the most popular marine
macroalgae growing worldwide. The sample collected was 5 kg in
weight and it was air dried under ambient conditions during a period of over 12 months. After that, visible contaminants such as
sand and shell particles were eliminated manually from the sample. Then the sample was cut and ground to a particle size of
<500 lm and studied by the above listed methods and procedures.
The ashing of macroalgae was conducted at 500 C for 2 h and 700,
900, 1100 and 1300 C for 1 h as the last temperature is the fluid
ash-fusion temperature of this sample. Breaking of the ceramic
crucibles and gentle handpicking under a binocular microscope
were applied to separate the fused material (slag) that was formed
at the maximum temperature. Despite that, a few and fine ceramic
particles from the crucibles were observed microscopically to
occur as contaminants in algae slag. These contaminants were
identified as mullite, plagioclase and quartz by XRD.
3. Results and discussion
3.1. General considerations about composition and properties of algae
and algae ash
The bulk chemical composition of algae and algae ash (AA)
includes proximate, ultimate and elemental analyses and they
are the initial characterization and simplified expression of these
complex systems [8]. The bulk chemical composition is an important characteristic; however, it is insufficient to fully understand
the composition, properties and behaviour of algae during processing. For that purpose, the abundance, origin and performance of

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Table 4
Clarke contents (worldwide average element concentrations) and enrichment/depletion factors (EDF) of 77 elements for coals, plants and algae, ppm on dry basis.
Clarke for plantsc

Clarke for algaed

EDF for plants/coalse

EDF for algae/coalsf

EDF for algae/plantsg

1. Non-metal elements
B
52a
Br
5.2a
C
630 000b
Cl
180a
F
88a
H
52 000b
I
1.9a
N
13 000b
O
160 000b
P
230a
S
18 000b
Si
27 000b

51
9.5
449 667
2000
1.25
65 000
1.7
29 000
425 000
2400
2500
600

110
870
306 250
32 350
4.75
43 667
710
37 000
470 000
5700
15 000
57 375

0.98
1.83
0.71
11.11
0.01
1.25
0.89
2.23
2.66
10.43
0.14
0.02

2.12
167.31
0.49
179.72
0.05
0.84
373.68
2.85
2.94
24.78
0.83
2.13

2.16
91.58
0.68
16.18
3.80
0.67
417.65
1.28
1.11
2.38
6.00
95.63

2. Lithophile elements
Al
15 000b
Ba
150a
Be
1.6a
Ca
4600b
Ce
23a
Cs
1.0a
Dy
2.1a
Er
0.93a
Eu
0.47a
Gd
2.7a
Hf
1.2a
Ho
0.54a
K
1800b
La
11a
Li
12a
Lu
0.20a
Mg
1100b
Mo
2.2a
Na
800b
Nb
3.7a
Nd
12a
Pr
3.5a
Rb
14a
Sm
2.0a
Sr
110a
Ta
0.28a
Tb
0.32a
Tm
0.31a
W
1.1a
Y
8.4a
Yb
1.0a
Zr
36a

232
39
0.001
11 500
0.5
0.2
0.03
0.02
0.0145
0.04
0.05
0.008
13 100
0.1425
0.15
0.003
2167
0.51
563
0.22
0.2
0.05
35
0.0228
38
0.001
0.008
0.0028
0.135
0.2
0.02
0.327

61
20.5

<0.01
0.14

0.26
0.53

2.04

0.82

0.09

0.43

22.78
0.91
0.48

3.13
70.18
38.00

5.61
0.20
48.75

2.85
0.88
69.27

0.69

0.28

10.00

28.95

3.0

0.02
0.26
<0.01
2.50
0.02
0.20
0.01
0.02
0.03
0.01
0.04
0.01
7.28
0.01
0.01
0.02
1.97
0.23
0.70
0.06
0.02
0.01
2.50
0.01
0.35
<0.01
0.03
<0.01
0.12
0.02
0.02
<0.01

0.08

9.17

3. Siderophile elements
Co
5.1a
Cr
16a
Fe
13 000b
Mn
86a
Ni
13a
Sc
3.9a
Ti
800a
V
25a

0.29
0.63
140
387
2.03
0.014
3.0
0.93

0.6
1.15
848
27.2
2.25
1.0
13.5
2.0

0.06
0.04
0.01
4.50
0.16
<0.01
<0.01
0.04

0.12
0.07
0.07
0.32
0.17
0.26
0.02
0.08

2.07
1.83
6.06
0.07
1.11
71.43
4.50
2.15

35

0.02
0.04
0.23
0.81
0.01
<0.01
0.58
0.03
0.23
0.09
0.08
0.22
<0.50
0.08
3.42

4.22

233.33

3.95
0.66
0.06

17.40
0.81
4.67

0.30

0.52

0.67

2.84

0.65
1.18

7.64
5.26

3.91

1.14

Element

Clarke for coalsa,b

4. Chalcophile elements (metals and semi-metals)


As
8.3a
0.15
Bi
0.97a
0.035
Cd
0.22a
0.05
Cu
16a
13
a
Ga
5.8
0.075
a
Ge
2.2
0.01
a
Hg
0.10
0.0575
In
0.031a
0.001
Pb
7.8a
1.83
Sb
0.92a
0.08
Se
1.3a
0.11
a
Sn
1.1
0.247
b
Te
<0.1
0.05
a
Tl
0.63
0.05
Zn
23a
78.7

9375
0.085

41 000
10
5.7
6175
0.45
39 000

9.7
1100

0.87
10.5
0.35
0.03
5.2
0.84
1.3

90

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133


Table 4 (continued)
Clarke for plantsc

Clarke for algaed

EDF for plants/coalse

5. Radioactive elements
Th
3.3a
U
2.4a

0.005
0.024

1.0

<0.01
0.01

0.30

200.00

6. Noble elements
Ag
0.095a
Au
0.0037a
Ir
0.002a
Os
<0.001b
Pd
0.0074a
Pt
0.035a
Rh
<0.001b
Ru
<0.001b

0.11
0.001
0.0001
0.000015
0.001
0.00005
0.0001
0.0026

0.3
0.01

1.16
0.27
0.05
<0.02
0.14
<0.01
<0.10
>2.60

3.16
2.70

2.73
10.00

Element

Clarke for coalsa,b

EDF for algae/coalsf

EDF for algae/plantsg

Note: The mineralogical classification of elements [62] was used.


The bold font represents values >1.0.
a
Clarke for coals worldwide [65].
b
Clarke for US coals [63].
c
Clarke for plants based on the mean contents of: world reference plant (worldwide average of all parts of all plants) [64]; angiospermous plants worldwide [30]; and
gymnospermous plants worldwide [30].
d
Clarke for algae based on the mean contents of unicellular, multicellular, brown and diatom algae worldwide [30].
e
EDF is defined as a ratio of the Clarke element content in plants to the respective Clarke value in coals.
f
EDF is defined as a ratio of the Clarke element content in algae to the respective Clarke value in coals.
g
EDF is defined as a ratio of the Clarke element content in algae to the respective Clarke value in plants.

modes of element occurrence (phases and minerals) in algae and


AA are required [9,11]. The combined chemical and phasemineral composition is a fundamental code that depends on various factors and definite properties, quality and application perspectives, as well as technological and environmental problems
related to any fuel [8].
The composition and properties of algae and AA are influenced
by many factors including: (1) algae resource (algae species, part of
plant, algae age, environmental conditions, growing processes and
cultivation methods, fertiliser doses used, harvesting time, collection technique, transport, storage, pollution, others); (2) algae processing (fuel preparation, thermochemical conversion technology
and conditions, collection and cleaning equipment); and (3) transport and storage of AA. Therefore, algae and AA have variable
chemical and phase-mineral composition and properties [11].
Algae, similar to other biomasses, is a complex heterogeneous
mixture of organic matter and, to a lesser extent, inorganic matter
with polycomponent and variable composition, and contains intimately associated solid and fluid phases with different contents
and origin. Organic matter consists of: (1) non-crystalline ingredients (hemicellulose, cellulose, lignin, proteins, lipids, others); and
(2) crystalline organic minerals (oxalates, some cellulose, others).
Inorganic matter contains: (1) crystalline mineral species from different mineral classes (silicates, oxyhydroxides, sulphates, phosphates, carbonates, chlorides, nitrates, others); (2) semicrystalline and poorly crystallized mineraloids (some silicates,
phosphates, hydroxides, chlorides and others); and (3) amorphous
phases (various non-crystalline species, silicates, others). The fluid
matter in algae is mostly inorganic and includes fluid, liquid and
gas constituents (moisture, gas and gasliquid inclusions) associated with both organic and inorganic matter. The phases in algae
originate from natural (authigenic and detrital) and anthropogenic
(technogenic) processes during pre-syngenesis, syngenesis, epigenesis and post-epigenesis of algae according to the main formation
process and place, time and mechanism of phase formation [9,11].
Algae ash is the solid residue that results from the combustion
of algae biomass and includes: (1) laboratory produced lowtemperature ash in oxygen plasma at 100250 C; (2) laboratory
generated high-temperature ash (HTA) in air normally above
500 C and at regulated temperatures; (3) industrially produced
bottom ash (from dry-ash discharge boilers) or slag (from melt discharge boilers); and (4) industrially generated fly ash (from flue
gas discharge systems); as the last two ash types are produced in

combustion installations at temperatures commonly between


800 and 1600 C. The laboratory and industrial biomass ashes are
formed under different conditions; however, they show similar
ash formation mechanisms and phase-mineral transformations,
despite some peculiarities, as described for coal ashes [11,12].
Algae ash, similar to other biomass ashes, is a complex heterogeneous mixture of inorganic matter and, to a lesser extent,
organic matter with polycomponent and variable composition
and particle morphology, and contains intimately associated solid
and fluid phases with different contents and origin. Inorganic matter consists of: (1) non-crystalline (amorphous) glass particles; and
(2) crystalline to semi-crystalline (mineral) crystals, grains and
aggregates of various minerals or poorly crystallized mineraloids
(sulphates, chlorides, oxyhydroxides, carbonates, silicates, phosphates, nitrates, others). Organic matter contains: (1) crystalline
(mineral) crystals, grains and aggregates of organic minerals (oxalates, others); and (2) non-crystalline (amorphous) to semicrystalline char including semi-coked, coked, soot and tar particles.
The fluid matter in AA is mostly inorganic and includes fluid, liquid
and gas (moisture and gas and gasliquid inclusions) associated
with both inorganic and organic matter. The phases and minerals
in AA originate from natural and technogenic processes and can
be classified by origin as: (1) primary, namely pre-existing or original minerals and phases in algae that have undergone no phase
transformations during combustion (mostly refractory silicates,
oxyhydroxides and phosphates); (2) secondary such as new phases
formed during combustion process (species from all mineral
classes plus glass and char); and (3) tertiary, namely new minerals
or phases formed during transport and storage of AA (mainly carbonates and hydroxides) according to the main formation process
and place, time and mechanism of phase formation [3,11].
3.2. Common trends about the composition and properties of algae and
algae ash
The reference and own biomass, algae and coal data [35,714,
1618,20,22,27,30,36,38,4245,47,52,53,57,6265] were used to
characterize the composition and properties of algae and AA. The
above data are summarized (Tables 410 and Figs. 16 plus some
results from [3,814]) and applied herein to find some common
trends based on the mean values. These data show that the
algae biomass in comparison with the terrestrial biomass normally
has:

10

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Table 5
Clarke contents (worldwide average element concentrations) and enrichment/depletion factors (EDF) of 73 elements for coal ashes, plant ashes and algae ashes, ppm on dry basis.
Element

Clarke for coal


ashesa,b

Clarke for plant


ashesc

Clarke for algae


ashesd

EDF for plant ashes/coal


ashese

EDF for algae ashes/coal


ashesf

EDF for algae ashes/plant


ashesg

1. Non-metal elements
B
335a
Br
32a
Cl
1440a
F
605a
I
12.6a
P
1350a
S
137 400b
Si
206 100b

1041
194
40 816
26
35
48 980
51 020
12 245

414
3271
121 617
18
2669
21 429
56 391
215 695

3.11
6.06
28.34
0.04
2.78
36.28
0.37
0.06

1.24
102.22
84.46
0.03
211.83
15.87
0.41
1.05

0.40
16.86
2.98
0.69
76.26
0.44
1.11
17.61

2. Lithophile elements
Al
114 500b
Ba
940a
Be
9.4a
Ca
35 100b
Ce
130a
Cs
6.6a
Dy
14a
Er
5.5a
Eu
2.5a
Gd
16a
Hf
8.3a
Ho
4.0a
K
13 700b
La
69a
Li
66a
Lu
1.2a
Mg
8400b
Mo
14a
Na
6100b
Nb
20a
Nd
67a
Pr
20a
Rb
79a
Sm
13a
Sr
740a
Ta
1.7a
Tb
2.1a
Tm
2.0a
W
6.9a
Y
51a
Yb
6.2a
Zr
210a

4735
796
0.02
234 694
10
4.1
0.6
0.4
0.3
0.8
1.0
0.2
267 347
2.9
3.1
0.06
44 224
10
11 490
4.5
4.1
1.0
714
0.5
776
0.02
0.2
0.06
2.8
4.1
0.4
6.7

229
77

<0.01
0.08

0.05
0.10

1.00

0.15

0.05

0.07

11.25
0.55
0.32

0.58
13.10
6.77

2.76
0.12
24.04

0.52
0.17
12.76

0.46

0.05

5.59

5.33

11

0.04
0.85
<0.01
6.69
0.08
0.62
0.04
0.07
0.12
0.05
0.12
0.05
19.51
0.04
0.05
0.05
5.26
0.71
1.88
0.23
0.06
0.05
9.04
0.04
1.05
0.01
0.10
0.03
0.41
0.08
0.06
0.03

0.05

1.64

3. Siderophile elements
Co
32a
Cr
100a
Fe
99 200b
Mn
490a
Ni
76a
Sc
23a
Ti
4650a
V
155a

5.9
13
2857
7898
41
0.3
61
19

2.3
4.3
3188
102
8.5
3.8
51
7.5

0.18
0.13
0.03
16.12
0.54
0.01
0.01
0.12

0.07
0.04
0.03
0.21
0.11
0.17
0.01
0.05

0.39
0.33
1.12
0.01
0.21
12.67
0.84
0.39

132

0.07
0.12
0.83
2.88
0.05
0.01
1.56
0.13
0.79
0.25
0.25
0.78
>1.25
0.20
11.47

2.81

42.58

2.75
0.42
0.04

3.30
0.15
0.87

0.15

0.09

0.43

0.54

0.36
0.77

1.45
0.98

2.41

0.21

0.18

38.00

4. Chalcophile elements (metals and semi-metals)


As
47a
3.1
Bi
5.9a
0.7
a
Cd
1.2
1.0
Cu
92a
265
Ga
33a
1.5
Ge
15a
0.2
Hg
0.75a
1.17
a
In
0.16
0.02
a
Pb
47
37
a
Sb
6.3
1.6
Se
8.8a
2.2
Sn
6.4a
5.0
Te
<0.8b
1.0
Tl
4.9a
1.0
a
Zn
140
1606
5. Radioactive elements
Th
21a
U
16a

0.1
0.5

35 244
0.3

154 135
38
21
23 214
1.7
146 617

36
4135

3.3
39
1.3
0.11
20
3.2
4.9

338
3.8

<0.01
0.03

11

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133


Table 5 (continued)
Element

Clarke for coal


ashesa,b

6. Noble elements
Ag
0.61a
Au
0.022a
Ir
0.010a
Os
<0.008b
Pd
0.037a
Pt
0.13a
Rh
<0.008b
Ru
<0.008b

Clarke for plant


ashesc

Clarke for algae


ashesd

EDF for plant ashes/coal


ashese

2.24
0.02
0.002
0.0003
0.02
0.001
0.002
0.05

1.13
0.04

3.67
0.91
0.20
>0.04
0.54
0.01
>0.25
>6.25

EDF for algae ashes/coal


ashesf

1.85
1.82

EDF for algae ashes/plant


ashesg

0.50
2.00

Note: The mineralogical classification of elements [62] was used.


The bold font represents values >1.0.
a
Clarke for coal ashes worldwide [65].
b
Clarke for US coal ashes recalculated from coal data for 13.1% ash yield [63].
c
Clarke for plant ashes based on the mean contents of: world reference plant (worldwide average of all parts of all plants) [64]; angiospermous plants worldwide [30]; and
gymnospermous plants worldwide [30], recalculated from plant data for 4.9% ash yield [8].
d
Clarke for algae ashes based on the mean contents of unicellular, multicellular, brown and diatom algae ashes worldwide [30], recalculated from algae data for 26.6% ash
yield.
e
EDF is defined as a ratio of the Clarke element content in plant ashes to the respective Clarke value in coal ashes.
f
EDF is defined as a ratio of the Clarke element content in algae ashes to the respective Clarke value in coal ashes.
g
EDF is defined as a ratio of the Clarke element content in algae ashes to the respective Clarke value in plant ashes.

(1) Higher values of ash, bulk density, combustion temperature,


electrical conductivity, extractives, fixed carbon, hemicellulose, inorganic matter, lipids, moisture, nucleic acids, pH,
proteins, water-soluble fraction, Ag, As, Au, B, Be, Br, Cd,
Ce, Cl, Co, Cr, Dy, Er, Eu, F, Fe, Ga, Gd, Ge, Hf, Ho, I, K, La, Li,
Lu, Mg, N, Na, Nd, Ni, O, P, Pb, Pr, S, Sb, Sc, Se, Si, Sm, Sn,
Sr, Ta, Tb, Th, Ti, Tm, U, V, Y, Yb, Zn, and Zr.
(2) Lower values of carbohydrates, cellulose, cellulose crystallinity index, heating value, initial ignition temperature,
lignin, organic matter, reactivity, volatile matter, Al, Ba, Bi,
C, Ca, Cs, Cu, H, Hg, Mn, Mo, Nb, Rb, and W.
On the other hand, the summarized data reveal that AA in comparison with the terrestrial biomass ash commonly has:
(1) Higher values of bulk density, chlorides, inorganic amorphous matter, silicates, oxyhydroxides, sulphates, watersoluble fraction, As, Au, Be, Br, Cd, Cl, Fe, Ge, I, La, Li, Lu,
Na, S, Sc, Se, Si, Sm, Sr, Ta, Th, and Zr.
(2) Lower values of ash-fusion temperatures (especially the
deformation temperature), carbonates, pH, phosphates, Ag,
Al, B, Ba, Bi, Ca, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, F, Ga, Gd, Hf,
Hg, Ho, K, Mg, Mn, Mo, Nb, Nd, Ni, P, Pb, Pr, Rb, Sb, Sn, Tb,
Ti, U, V, W, Y, Yb, and Zn.
The summarized data also show that the algae biomass in comparison with the coal normally has:
(1) Higher values of ash, moisture, reactivity, volatile matter, Ag,
As, Au, B, Be, Br, Ca, Cd, Cl, I, K, Mg, N, Na, O, P, Si, Sn, Sr, and Zn.
(2) Lower values of ash-fusion temperatures, bulk density, combustion temperature, fixed carbon, heating value, initial ignition temperature, Al, Ba, Bi, C, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, F,
Fe, Ga, Gd, Ge, H, Hf, Hg, Ho, La, Li, Lu, Mn, Mo, Nb, Nd, Ni, Pb,
Pr, Rb, S, Sb, Sc, Se, Sm, Ta, Tb, Th, Ti, Tm, U, V, W, Y, Yb, and
Zr.
Finally, the summarized data reveal that AA in comparison with
the coal ash commonly has:
(1) Higher values of carbonates, chlorides, oxyhydroxides, phosphates, sulphates, water-soluble fraction, Ag, As, Au, B, Br,
Ca, Cd, Cl, I, K, Mg, Na, P, Si, Sr, and Zn.

(2) Lower values of ash-fusion temperatures, bulk density, silicates, Al, Ba, Be, Bi, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, F, Fe, Ga,
Gd, Ge, Hf, Hg, Ho, La, Li, Lu, Mn, Mo, Nb, Nd, Ni, Pb, Pr, Rb,
S, Sb, Sc, Se, Sm, Sn, Ta, Tb, Th, Ti, Tm, U, V, W, Y, Yb, and Zr.
The above listed trends have a leading importance for the
advanced and sustainable utilization of algae as biofuel and algae
co-processing with terrestrial biomass and coal. These important
trends and their advantages and disadvantages during algae conversion are described below.

3.3. Chemical composition and properties of algae and algae ash


3.3.1. Moisture
The higher moisture content of algae in comparison with the
terrestrial biomass is one of the major disadvantages of this fuel
[14]. This characteristic for the terrestrial biomass (as collected)
has contents normally in the range from 10% to 63% [8,9]. Algae
have higher contents of water as these values are commonly in
the range from 70% to 90% (fresh basis) [23,56]. In contrast, the
moisture occurrence in peat and coal is commonly in the more narrow range up to 20% [14]. Moisture is a mineralised aqueous solution containing various cations, anions or non-charged species in
cell fluid of biomass and its role has been characterized in detail
earlier ([9] and references therein). It is well known that annual
and fast growing crops show the highest contents of water, inorganic matter and elements such as Ca, Cl, K, Mg, N, Na, P and S.
These are typical mobile elements not only in the plant physiology,
but also in the natural water system. The minerals tend to precipitate in the plants during growing and after harvesting. There is
intensive epigenetic mineral precipitation from a saturated solution due to moisture evaporation after biomass harvesting and
during biomass drying. This process results in consecutive formation of water-soluble: (1) phosphates; (2) carbonates; (3) sulphates; (4) chlorides; and (5) nitrates, which are normally a
general sequence of precipitation from less soluble to highly soluble minerals in the water system. Such epigenetic mineral formations are the reason for enhanced leaching of the above listed
elements from biomass harvested and left in the field for a prolonged period of time [9]. Most of the above listed processes are
even more characteristic of algae than terrestrial biomass because
the fluid matter plays a very important role for the composition of
algae due to the high content of moisture and inorganic matter,

12

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Table 6
Composition and properties of algae and algae ashes (macro, micro, green, blue-green, brown, red, diatom, marine and freshwater), wt.% on dry basis (indicated otherwise).
Characteristic

Mean

Minimum

Maximum

Proximate analysis of algae (macro, green, brown, red, marine)


Volatile matter
Ash yield
Fixed carbon
Sum

52.4
26.6
21.0
100.0

37.2
13.1
9.0

61.7
42.8
29.2

Ultimate analysis of algae (macro, micro, green, blue-green, brown, red, marine, freshwater),
dry ash-free basis
C
O
H
N
S
Sum

45.1
40.4
7.3
5.6
1.62
100.02

38.6
26.3
4.6
1.1
0.47

54.4
53.1
12.7
12.4
3.30

Ash-forming elements in algae (macro, micro, green, brown, diatom, marine, freshwater)
K
Na
Cl
Si
Ca
Sb
P
Mg
Fe
Al
Ti

3.66
3.51
3.11
2.30
1.24
1.19
0.82
0.72
0.157
0.125
0.0040

0.69
0.54
0.47
0.12
0.38
0.34
0.10
0.13
0.003
0.006
0.0012

11.58
7.06
6.00
20.0
3.84
2.42
2.50
1.50
0.375
0.300
0.0071

Ash-forming elements in algae ash (macro, micro, green, brown, red, diatom, marine)
K
Na
Cl
S
Ca
Si
Mg
P
Fe
Al
Ti

21.97
13.41
11.44
7.04
5.00
4.17
2.78
1.22
1.20
0.97
0.09

5.40
9.00
1.77
4.51
0.96
0.56
0.49
0.31
0.19
0.02
0.01

42.96
18.28
22.56
9.84
13.61
7.52
5.64
3.76
3.36
3.03
0.32

Ash-forming oxides in algae ash (macro, green, brown, red, marine)


SiO2
SO3
Cl2O
K2O
Na2O
CaO
MgO
P2O5
Fe2O3
Al2O3
TiO2
Sum

20.38
18.81
16.13
15.71
13.56
7.28
3.42
1.80
1.55
1.23
0.13
100.00

1.81
12.71
2.18
7.70
7.58
0.81
0.78
0.52
0.26
0.04
0.01

36.09
29.02
27.75
35.61
25.21
22.48
7.83
3.61
3.63
4.32
0.39

Organic compounds in algae (macro, micro, green, blue-green, brown, red, diatom, marine,
freshwater), normalized to 100%
Proteins
Carbohydrates
Lipids
Nucleic acids
Sum
Structural organic components in algae (macro, micro, green, blue-green, brown, red, marine),
normalized to 100%
Hemicellulose
Cellulose
Lignin
Sum
Structural organic components and extractives in algae (macro, micro, green, blue-green,
brown, red, marine), normalized to 100%
Hemicellulose
Cellulose
Extractives
Lignin
Sum
Ash fusion temperatures of algae (macro, green, brown, red, marine), C

Samplesa
12

[13,42,44,45]

20

[5,17,30,44,45,47]

33

[5,13,30,36,38,43,44,53]

16

[13,30,38,45]

12

[13,30,38,45]

170
42.8
29.9
23.4
3.9
100.0

78.5
14.1
7.4
100.0

73.1
13.0
7.5
6.4
100.0

6.0
4.0
0.9
1.0

57.7
0.0
0.0

47.8
0.0
0.5
0.0

Reference used

[4,5,7,16,18,20,22,27,57]

71.0
83.6
77.0
6.0
9

[57]

[57]

[45]

100.0
28.9
30.8

90.8
28.1
17.2
25.5

13

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133


Table 6 (continued)
Characteristic

Mean

Minimum

Maximum

Initial deformation temperature


Spherical temperature
Hemispherical temperature
Fluid temperature

924
1008
1216
1296

747
822
1041
1227

1135
1175
1415
1434

Calorific value of algae (macro, micro, green, blue-green, brown, red, marine, freshwater),
MJ kg 1
Higher heating value
Lower heating value
a
b

Samplesa

42
17.4
10.9

7.9
7.9

Reference used

[5,17,42,44,45,47,52,57]

24.0
14.8

Some of these data are mean values from numerous determinations for a given algae variety.
Recalculated from ultimate analysis of S for 26.6% ash yield.

great total mineralisation and different chemical composition of


these solutions (see Section 3.3.6). The high moisture content of
algae has numerous negative effects such as: (1) problems during
pre-treatment and upgrading (drying, grinding, separation, baling,
pelletization, briquetting, torrefaction, others); (2) complications
during thermochemical conversion (excluding liquefaction, gasification, alcoholic fermentation and anaerobic digestion), namely
lowering calorific value, poor ignition, reducing the combustion
temperature and combustion efficiency, longer residence time in
combustion units, flame stability problems, delaying the release
of volatiles, forming a large quantity of flue gas and fumes, incomplete cracking of the hydrocarbons, increasing unburned C levels in
ash, and a need for larger equipment dimensions; (3) precipitation
of chlorides, sulphates, carbonates, nitrates and phosphates during
drying; (4) enhanced leaching (Ca, Cl, K, Mg, Na, P, S, trace elements) during storage and processing; and (5) deterioration due
to the microbial activity and promoting health risk resulted from
fungus and moulds proliferation ([14] and references therein).
Finally, the raw biomass (including algae) with >3050% moisture
content does not burn before the partial evaporation of some moisture. 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 630%
for different biomass fuels ([14] and references therein).
3.3.2. Ash yield and inorganic matter
The higher ash content of algae compared to the terrestrial biomass is a typical characteristic and one of the biggest disadvantages for the algae processing [14]. The ash yield (dry basis) is in
the interval of 0.146.3% (mean 6.8%) for terrestrial biomass [8]
and 13.142.8% (mean 26.6%) for algae (Table 6 and Fig. 1). Algae
normally have much higher ash content than terrestrial biomass
because the former fuel has different composition, organic structure and rapid metabolism which takes up much more nutrients
during the growing periods ([3] and references therein). For coal,
the ash contents (dry basis) are in the range of 652% (commonly
630% and mean about 21%) and normally show much higher values than terrestrial biomass and comparable values to algae (Fig. 1
and [8]). It should be stated that the terms ash, inorganic matter
and mineral matter of algae are not synonymous because they
comprise constituents with different nature and quantity [8]. The
ash yield itself brings relatively limited information when the composition, abundance and origin of the algae constituents are not
considered. Hence, the ash should always be interpreted together
with the genesis of constituents in algae [8]. It can be seen
(Fig. 4) that the algae inorganic matter belong to the K type with
low acid tendency (K-LA sub-type) and their position is closer to
the inorganic matter mostly of the sub-group of herbaceous and
agricultural residues [8,12]. It was stated 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 [14]. For example, the high ash

content of algae is less desirable and has a great contribution for


poorer fuel quality and problems due to: (1) decreasing heating
value; (2) increasing concentrations of trace elements; (3) complicated thermochemical and biochemical conversions; (4) more fouling, deposition, agglomeration, slagging, corrosion and erosion
problems; (5) increasing operating costs concerning algae harvesting, transport and processing, gas-cleaning technologies, as well as
ash transport, disposal and utilization; (6) more fuel contamination by sand, shells, soil, dirt, rainfall and wind during algae growing, harvesting, transport or processing ([14] and references
therein); and others (see below).
3.3.3. Volatile matter, reactivity and initial ignition and combustion
temperatures
The lower values of volatile matter (VM), initial ignition temperature and reactivity, and higher value of combustion temperature compared to the terrestrial biomass are characteristic
features of algae. These observations have both disadvantages
and advantages for algae thermochemical conversion [14]. The
high VM content (especially combustible VM) and low initial ignition and combustion temperatures are among the greatest advantages of biomass for thermochemical conversion because they
induce the highly reactive nature of this fuel ([14] and references
therein). It is widely accepted that the combustible gases released
from the thermal decomposition of biomass include dominantly
species such as CH4, C2H2, CO, H2, H2S, tars and other mainly light
hydrocarbons ([11] and references therein). However, algae in
comparison with the terrestrial biomass normally show lower
VM content (mean 52.4% versus 75.4% dry basis in Table 6, Fig. 1
and [8]), initial ignition temperature (200 C) and reactivity values,
and higher combustion temperatures (200800 C) as described in
Section 3.6. These algae features may cause: (1) reduced production of combustible gas; (2) hindered ignition, devolatilization
and burning; (3) less flaming and more char combustion; and (4)
poor burnout with higher unburned char in the ash during thermochemical conversion (see Section 3.6). On the other hand, a synergic benefit may be expected during co-firing of coal (mean 30.8%
VM, dry basis [8]) with algae because the higher VM contents in
the latter fuel can provide a better initial ignition and more stable
flame for the blended fuel [14].
3.3.4. Bulk density, calorific value and energy density
The bulk density (loose basis) of algae (954 kg m 3 Table 7) and
AA (430 kg m 3 Table 7) is higher in comparison with the
terrestrial biomasses (250889 kg m 3 [9]) and their ashes (80
270 kg m 3 [3]). The high bulk density of algae and AA is due to
the abundance of heavy inorganic matter in them (see Sections
3.4.2 and 3.5, and Table 10). Such higher values are typical peculiarities and significant disadvantages because the big differences
between the density of organic and inorganic particles can induce
substantial particles separation during algae and AA processing.
The lower calorific value of algae (mean 17 MJ kg 1 higher heating

14

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Table 7
Composition and properties of marine macroalgae (sea lettuce) based on [12,13,57], wt.% on air-dried basis (indicated otherwise).
Characteristic
Source
Collection time
Note
Size reduction (mm)
Organic type
Inorganic type
Inorganic sub-type

Sea lettuce (macro, green, marine algae, Ulva lactuca)


Tsarevo, Bulgaria
08.2009
Cleaned from sand and shell grains
<0.5
HCL
K
K-LA

1. Algae
Volatile matter (db)
Fixed carbon (db)
Ash yield (db)
Sum
Higher heating value (MJ kg 1)a
Initial ignition temperature by DTATGA (C)
Combustion temperature by DTATGA (C)
Bulk density (loose) (kg m 3)
Bulk density (shaken) (kg m 3)
pH of leachate (solidliquid = 1:10 mass ratio)
Electrical conductivity of leachate (mS/cm)
Dry water-soluble residue
Cellulose (daf)a
Hemicellulose (daf)a
Lignin (daf)a
Extractives (daf)a
Sum
Cellulose (daf)a
Hemicellulose (daf)a
Lignin (daf)a
Sum
Starcha
Proteinsa
Ca
S
Na
Cl
K
Mg
Si
Al
Fe
P
Ti
Mn

47.4
24.4
28.2
100.0
15.9
200
200800
954
1250
6.75
19.81
15.1
13.9
73.3
5.7
7.1
100.0
15.0
78.9
6.1
100.0
0.7
12.0
3.84
2.78
2.54
2.35
1.52
1.13
0.637
0.127
0.118
0.1034
0.0056
0.0047

2. Algae ash (500 C)


Ash yield (500 C/2 h)
Ash yield (700 C/1 h)
Ash yield (900 C/1 h)
Ash yield (1100 C/1 h)
Ash yield (1300 C/1 h)
Fluid ash-fusion temperature observed (C)
Fluid ash-fusion temperature by DTA (C)
Bulk density (loose) (kg m 3)
pH of leachate (solidliquid = 1:50 mass ratio)
Dry water-soluble residue
Ca
S
Na
Cl
K
Mg
Si
Al
Fe
P
Ti
Mn
SO3
CaO
Na2O
Cl2O
MgO
K2O
SiO2
Al2O3

28.24
23.58
20.50
17.17
11.69
61300
1240
430
8.4
42.8
13.61
9.84
9.00
8.32
5.40
4.00
2.26
0.45
0.42
0.37
0.0174
0.0167
28.49
22.06
14.07
11.84
7.69
7.56
5.60
0.98

15

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133


P2O5
Fe2O3
TiO2
MnO
Sum of oxides

0.97
0.69
0.03
0.02
100.00

Abbreviations: daf, dry ash-free basis; db, dry basis; DTA, differential-thermal analysis; TGA, thermo-gravimetric analysis.
a
Based on [57].

Table 8
Contents and enrichment/depletion factors (EDF) of 60 elements for coals, plants, algae and marine macroalgae (sea lettuce), ppm on dry basis.
Clarke for plantsc

Clarke for algaed

Sea
lettucee

EDF for sea lettuce/coalsf

1. Non-metal elements
B
52a
Cl
180a
P
230a
S
18 000b
Si
27 000b

51
2000
2400
2500
600

110
32 350
5700
15 000
57 375

2440
23 462
1034
27 749
6375

46.92
130.34
4.50
1.54
0.24

47.84
11.73
0.43
11.10
10.63

22.18
0.73
0.18
1.85
0.11

2. Lithophile elements
Al
15 000b
Ba
150a
Be
1.6a
Ca
4600b
Ce
23a
Cs
1.0a
Dy
2.1a
Er
0.93a
Eu
0.47a
Gd
2.7a
Hf
1.2a
Ho
0.54a
K
1800b
La
11a
Li
12a
Lu
0.20a
Mg
1100b
Mo
2.2a
Na
800b
Nb
3.7a
Nd
12a
Pr
3.5a
Rb
14a
Sm
2.0a
Sr
110a
Ta
0.28a
Tb
0.32a
Tm
0.31a
W
1.1a
Y
8.4a
Yb
1.0a
Zr
36a

232
39
0.001
11 500
0.5
0.2
0.03
0.02
0.0145
0.04
0.05
0.008
13 100
0.1425
0.15
0.003
2167
0.51
563
0.22
0.2
0.05
35
0.0228
38
0.001
0.008
0.0028
0.135
0.2
0.02
0.327

61
20.5

0.08
0.08
1.56
8.34
0.04
0.07
0.03
0.05
0.09
0.04
0.05
0.04
8.46
0.03
0.30
0.15
10.27
0.20
31.74
0.01
0.03
0.03
0.51
0.08
2.93
0.04
0.03
0.06
0.08
0.04
0.08
0.03

5.47
0.31
2500.00
3.34
1.78
0.35
2.00
2.50
2.76
2.50
1.20
2.50
1.16
2.25
24.00
10.00
5.21
0.88
45.10
0.18
1.95
1.80
0.20
7.02
8.47
10.00
1.25
7.14
0.67
1.70
4.00
3.03

20.79
0.59

3.0

1268
12
2.5
38 378
0.89
0.07
0.06
0.05
0.04
0.10
0.06
0.02
15 233
0.32
3.6
0.03
11 293
0.45
25 392
0.04
0.39
0.09
7.1
0.16
322
0.01
0.01
0.02
0.09
0.34
0.08
0.99

3. Siderophile elements
Co
5.1a
Cr
16a
Fe
13 000b
Mn
86a
Ni
13a
Sc
3.9a
Ti
800a
V
25a

0.29
0.63
140
387
2.03
0.014
3.0
0.93

0.6
1.15
848
27.2
2.25
1.0
13.5
2.0

0.99
18.6
1192
47.1
11.8
0.37
49.1
9.2

0.19
1.16
0.09
0.55
0.91
0.09
0.06
0.37

3.41
29.52
8.51
0.12
5.81
26.43
16.37
9.89

1.65
16.17
1.41
1.73
5.24
0.37
3.64
4.60

35

1.6
<0.003
1.4
10.2
2.5
1.7
0.76
0.17
2.76
0.3
14.7

0.19
<0.003
6.36
0.64
0.43
0.77
0.10
0.18
2.12
0.27
0.64

10.67
<0.09
28.00
0.78
33.33
170.00
0.42
2.13
25.09
1.21
0.19

0.05

Element

Clarke for coalsa,b

4. Chalcophile elements (metals and semi-metals)


As
8.3a
0.15
Bi
0.97a
0.035
a
Cd
0.22
0.05
Cu
16a
13
Ga
5.8a
0.075
Ge
2.2a
0.01
Pb
7.8a
1.83
a
Sb
0.92
0.08
a
Se
1.3
0.11
a
Sn
1.1
0.247
Zn
23a
78.7

9375
0.085

41 000
10
5.7
6175
0.45
39 000

9.7
1100

0.87
10.5
0.35
5.2
0.84
1.3
90

EDF for sea lettuce/plantsg

EDF for sea lettuce/algaeh

4.09
0.82

0.37
0.03
0.63
1.83
1.00
0.65

0.73
0.29

0.33

1.61
0.97
7.14
0.15
3.29
0.23
0.16
(continued on next page)

16

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Table 8 (continued)
Clarke for plantsc

Clarke for algaed

Sea
lettucee

5. Radioactive elements
Th
3.3a
U
2.4a

0.005
0.024

1.0

0.06
0.12

0.02
0.05

12.00
5.00

0.06

6. Noble elements
Ag
0.095a
Au
0.0037a

0.11
0.001

0.3
0.01

0.25
0.05

2.63
13.51

2.27
50.00

0.83
5.00

Element

Clarke for coalsa,b

EDF for sea lettuce/coalsf

EDF for sea lettuce/plantsg

EDF for sea lettuce/algaeh

Note: The mineralogical classification of elements [62] was used.


The bold font represents values >1.0.
a
Clarke for coals worldwide [65].
b
Clarke for US coals [63].
c
Clarke for plants based on the mean contents of: world reference plant (worldwide average of all parts of all plants) [64]; angiospermous plants worldwide [30]; and
gymnospermous plants worldwide [30].
d
Clarke for algae based on the mean contents of unicellular, multicellular, brown and diatom algae worldwide [30].
e
Recalculated from algae ash data [13] for 28.2% ash yield.
f
EDF is defined as a ratio of the element content in sea lettuce to the respective Clarke value in coals.
g
EDF is defined as a ratio of the element content in sea lettuce to the respective Clarke value in plants.
h
EDF is defined as a ratio of the element content in sea lettuce to the respective Clarke value in algae.
Table 9
Contents and enrichment/depletion factors (EDF) of 60 elements for coal ashes, plant ashes, algae ashes and marine macroalgae (sea lettuce) ash, ppm on dry basis.
Element

Clarke for coal


ashesa,b

Clarke for plant


ashesc

Clarke for algae


ashesd

Sea lettuce
ashe

EDF for sea lettuce


ash/coal ashesf

1. Non-metal elements
B
335a
Cl
1440a
P
1350a
S
137 400b
Si
206 100b

1041
40 816
48 980
51 020
12 245

414
121 617
21 429
56 391
215 695

8653
83 200
3668
98 400
22 606

25.83
57.78
2.72
0.72
0.11

8.31
2.04
0.07
1.92
1.85

20.90
0.68
0.17
1.74
0.10

2. Lithophile elements
Al
114 500b
Ba
940a
Be
9.4a
Ca
351 00b
Ce
130a
Cs
6.6a
Dy
14a
Er
5.5a
Eu
2.5a
Gd
16a
Hf
8.3a
Ho
4.0a
K
13 700b
La
69a
Li
66a
Lu
1.2a
Mg
8400b
Mo
14a
Na
6100b
Nb
20a
Nd
67a
Pr
20a
Rb
79a
Sm
13a
Sr
740a
Ta
1.7a
Tb
2.1a
Tm
2.0a
W
6.9a
Y
51a
Yb
6.2a
Zr
210a

4735
796
0.02
234 694
10
4.1
0.6
0.4
0.3
0.8
1.0
0.2
267 347
2.9
3.1
0.06
44 224
10
11 490
4.5
4.1
1.0
714
0.5
776
0.02
0.2
0.06
2.8
4.1
0.4
6.7

229
77

0.04
0.05
0.93
3.88
0.02
0.04
0.02
0.03
0.06
0.02
0.02
0.02
3.94
0.02
0.20
0.08
4.77
0.11
14.76
0.01
0.02
0.02
0.32
0.04
1.54
0.03
0.02
0.03
0.04
0.02
0.05
0.02

0.95
0.05
435.00
0.58
0.32
0.06
0.35
0.43
0.50
0.43
0.20
0.30
0.20
0.39
4.16
1.50
0.91
0.16
7.84
0.03
0.33
0.31
0.04
1.10
1.47
2.50
0.20
1.00
0.11
0.30
0.73
0.52

19.64
0.56

11

4497
43
8.7
136 091
3.15
0.26
0.21
0.17
0.15
0.34
0.20
0.06
54 019
1.13
12.9
0.09
40 047
1.60
90 043
0.14
1.37
0.31
25
0.55
1142
0.05
0.04
0.06
0.31
1.22
0.29
3.5

3. Siderophile elements
Co
32a
Cr
100a
Fe
99 200b
Mn
490a
Ni
76a
Sc
23a
Ti
4650a
V
155a

5.9
13
2857
7898
41
0.3
61
19

2.3
4.3
3188
102
8.5
3.8
51
7.5

3.5
66
4228
167
42
1.3
174
32.8

0.11
0.66
0.04
0.34
0.55
0.06
0.04
0.21

0.59
5.08
1.48
0.02
1.02
4.33
2.85
1.73

1.52
15.35
1.33
1.64
4.94
0.34
3.41
4.37

35 244
0.3

154 135
38
21
23 214
1.7
146 617

36
4135

EDF for sea lettuce


ash/plant ashesg

EDF for sea lettuce ash/


algae ashesh

3.86
0.87

0.35
0.03
0.61
1.73
0.94
0.61

0.69
0.28

0.32

17

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133


Table 9 (continued)
Element

Clarke for coal


ashesa,b

Clarke for plant


ashesc

4. Chalcophile elements (metals and semi-metals)


As
47a
3.1
Bi
5.9a
0.7
a
1.0
Cd
1.2
Cu
92a
265
Ga
33a
1.5
Ge
15a
0.2
Pb
47a
37
a
Sb
6.3
1.6
a
2.2
Se
8.8
a
Sn
6.4
5.0
Zn
140a
1606

Clarke for algae


ashesd

Sea lettuce
ashe

EDF for sea lettuce


ash/coal ashesf

132

5.6
<0.01
5.0
36
8.9
6.1
2.7
0.59
9.8
0.9
52

0.12
<0.01
4.17
0.39
0.27
0.41
0.06
0.09
1.11
0.14
0.37

1.81
<0.01
5.00
0.14
5.93
30.50
0.07
0.37
4.45
0.18
0.03

3.3
39
1.3
20
3.2
4.9
338

EDF for sea lettuce


ash/plant ashesg

EDF for sea lettuce ash/


algae ashesh

0.04
1.52
0.92
6.85
0.14
3.06
0.18
0.15

5. Radioactive elements
Th
21a
U
16a

0.1
0.5

3.8

0.23
0.43

0.01
0.03

2.30
0.86

0.06

6. Noble elements
Ag
0.61a
Au
0.022a

2.24
0.02

1.13
0.04

0.90
0.16

1.48
7.27

0.40
8.00

0.80
4.00

Note: The mineralogical classification of elements [62] was used.


The bold font represents values >1.0.
a
Clarke for coal ashes worldwide [65].
b
Clarke for US coal ashes [63].
c
Clarke for plant ashes based on the mean contents of: world reference plant (worldwide average of all parts of all plants) [64]; angiospermous plants worldwide [30]; and
gymnospermous plants worldwide [30], recalculated from plant data for 4.9% ash yield [8].
d
Clarke for algae ashes based on the mean contents of unicellular, multicellular, brown and diatom algae ashes worldwide [30], recalculated from algae data for 26.6% ash
yield.
e
Based on [13].
f
EDF is defined as a ratio of the element content in sea lettuce ash to the respective Clarke value in coal ashes.
g
EDF is defined as a ratio of the element content in sea lettuce ash to the respective Clarke value in plant ashes.
h
EDF is defined as a ratio of the element content in sea lettuce ash to the respective Clarke value in algae ashes.
Table 10
Contents (wt.%) of inorganic phases and minerals identified by XRD in marine macroalgae (sea lettuce) high-temperature ashes (HTAs) produced at different combustion
temperatures (C) based on [12].
Phase, mineral
1. Inorganic amorphous matter
2. Inorganic crystalline matter
2.1. Silicates
Quartz (Q)
2.2. Oxides and hydroxides
Lime (L)
Portlandite (Port)
2.3. Sulphates
Anhydrite (A)
2.4. Carbonates
Calcite (Cc)
2.5. Chlorides
Halite (Ha)
Sylvite (Sy)
Total

Formula

SiO2
CaO
Ca(OH)2
CaSO4
CaCO3
NaCl
KCl

HTA-500

HTA-700

HTA-900

HTA-1100

HTA-1300

Mean

42
58
1
1
7
0
7
11
11
19
19
20
18
2
100

24
76
2
2
19
2
17
20
20
5
5
30
26
4
100

51
49
2
2
10
1
9
18
18
0
0
19
17
2
100

68
32
0
0
1
1
0
31
31
0
0
0
0
0
100

100
0
0
0
0
0
0
0
0
0
0
0
0
0
100

57.0
43.0
1.0
1.0
7.4
0.8
6.6
16.0
16.0
4.8
4.8
13.8
12.2
1.6
100.0

basis in Table 6) in comparison with the terrestrial biomass (mean


about 1819 MJ kg 1 higher heating basis [14,44,66]) is a disadvantage for the thermochemical conversion of algae [14]. Hence,
the relatively low energy density of algae requires a 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 fuel. Different pre-treatment procedures such as drying, baling, chopping, milling, screening, pelletisation, briquetting,
and torrefaction are applied to: (1) increase the energy density; (2)
depress the self-ignition and static electric charge for particles
adhesion; and (3) improve the storage, resistance, grindability,
hydrophobicity, biological degradation, strength, transportation,
feeding and conversion of algae. It should be stated that the torrefaction process is an advanced approach for that purpose; however, the application of such low-temperature pyrolysis
technology seems to be much more economically perspective to

generate high-value products such as algae biochar than to produce a simple and cheap solid biofuel just for combustion and gasification ([14] and references therein).
3.3.5. Elemental composition
The elemental composition of algae may potentially include the
entire periodic table and comprises: major (>1.0%), minor
(0.11.0%) and trace (<0.1%) elements according to their concentrations (Tables 4 and 68). In decreasing order of abundance, the
major elements in algae are commonly O, C, Si, H, K, Na, N, Cl,
and S, while the minor elements normally include Ca, Mg, P, B,
Al, Fe, and Sr. The trace elements (TEs) in algae are the other elements identified. Nevertheless, there are cases among algae species
where the above order for certain elements is changeable. The
organic-forming elements in algae are normally O, C, H, and N
whereas the inorganic-forming elements are commonly Si, K, Na,

18

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Cl, S, Ca, Mg, P, B, Al, Fe, and Sr. However, some proportions from
the organic-forming elements also occur in inorganic matter, while
parts of the inorganic-forming elements are also present in organic
matter, similar to coal and other biomasses [8].
It was identified herein (Section 3.2) that many more elements
belonging to all elemental groups are enriched in the algae biomass
(54 elements) in comparison with the terrestrial biomass (14 elements). It is interesting to note that numerous elements mostly
from lithophile (Be, La, Li, Lu, Na, Sr, Ta), non-metal (B, Br, Cl, I, S,
Si) and chalcophile (As, Cd, Ga, Ge, Se) groups, and to a lesser
extent, siderophile (Cr, Sc, Ti), radioactive (Th) and noble (Au)
groups show the highest enrichment factors (above one order of
magnitude) in algae. In contrast, lower values only of some lithophile (Al, Ba, Ca, Cs, Mo, Nb, Rb, W), chalcophile (Bi, Cu, Hg), nonmetal (C, H) and siderophile (Mn) elements were commonly identified in the algae compared to the terrestrial biomass. Hence, it
can be supposed that the combination between the abundance of
some organic components (proteins, hemicellulose, lipids and
nucleic acids) and water-soluble inorganic matter (chlorides,
sulphates, carbonates, phosphates and nitrates) under brine mineralisation and neutral to slightly alkaline conditions are a favourable
environment for the concentration of many TEs in algae (see also
below). It seems that the organic components in algae play a role
of conducting and concentrating tissue for highly mineralised
solutions abundant in many mobile TEs [13].
It was also identified herein (Section 3.2) that lesser elements,
mainly among non-metal, lithophile and chalcophile groups, are
enriched in the algae (20 elements) in comparison with the coal
(48 elements). Elements such as Au, B, Br, Cl, I, K, Mg, Na, P, and
Sr show the highest enrichment factors (above one order of magnitude) in the algae. It is interesting to note that there is no enrichment of any siderophile elements in algae compared to coal
mainly due to: (1) the low concentration of Fe in algae; and (2)
the high content of Fe in coal and the typical abundance of Fe sulphides and Fe carbonates in the latter fuel, which are bearing and
concentrating minerals of siderophile TEs [9,67,68]. As a general
trend, only non-metals (especially halogen non-metals), alkaline
and alkaline-earth lithophile elements, noble elements, and some
chalcophile elements are commonly more enriched in algae than
in coal. The reason for that is mostly associated with lower amount
of organic matter and higher content of inorganic matter with
dominant authigenic origin in algae than in coal. In contrast, most
elements among lithophile, siderophile, chalcophile and radioactive groups, and only some non-metals are normally more enriched
in coal than in algae. The reason for that is mainly associated with
higher amount of organic matter and increased content of inorganic matter with dominant detrital nature in coal than in algae
[13].
The elements in AA can also be classified into major (>1.0%),
minor (0.11.0%) and trace (<0.1%) elements according to their elemental concentrations (Tables 57 and 9). In decreasing order of
abundance, the major elements in AA are commonly O, Si, K, Na,
Cl, S, Ca, Mg, P, while the minor elements normally include Al, Sr,
Br, Fe, and I. The trace elements in AA are the other elements identified. Nevertheless, there are cases among AAs where the above
order for certain elements is changeable. It should be stated that
organic-forming elements such as C, H, and N can also occur in
AA as unburned char, similar to coal ash and other BAs [8].
It was also identified herein (Section 3.2) that lesser elements,
mainly among non-metal and lithophile groups, are enriched in
AA (22 elements) in comparison with the terrestrial biomass ash
(41 elements). Elements such as As, Be, Br, Ge, I, La, Na, Sc, Si,
and Th show the highest enrichment factors (above one order of
magnitude) in AA and these elements are identical to those identified for algae. However, as mentioned above lesser elements are
enriched in AA compared to the terrestrial BA and this observation

is opposite to that for algae and terrestrial biomass. It is well


known that the bulk amount of ash forming constituents in terrestrial biomass (based on ash yield) is generally much lower in contrast to algae. Hence, the concentration of many elements in
terrestrial BA is higher than in AA and this trend is a result of:
(1) the enhanced enrichment of such elements in the former combustion residue due to the much higher contents of organic matter
in the terrestrial biomass; and/or (2) the high volatilization behaviour of the elements and their limited capture (particularly siderophile and chalcophile elements) in the ash during algae
combustion [13].
It can be seen (Section 3.2) that lesser elements, mainly among
non-metal, lithophile and chalcophile groups, are enriched in AA
(16 elements) in comparison with the coal ash (48 elements). Elements such as B, Br, Cl, I, K, Na, and P show the highest enrichment
factors (above one order of magnitude) in AA. These elements
enriched in AA compared to coal ash are identical to those identified for algae and coal (see above). It is again interesting to note
that there is no enrichment of any siderophile elements in AA compared to coal ash and the reasons for that were mentioned above.
3.3.5.1. Carbon and hydrogen. The lower values of C and H in algae
in comparison with the terrestrial biomass (Table 4 and Fig. 2) have
both disadvantages and advantages for the thermochemical processing of algae ([14] and references therein). For example, the
low contents of C and H have a direct negative relationship with
the calorific value of algae [14]. On the other hand, the low value
of C has significant benefit for reducing CO2 emissions during algae
conversion. 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 benefit of biomass combustion [69].
However, the incomplete biomass combustion can also lead to
generation 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
required ([14] and references therein). Finally, the low content of
H in algae is a disadvantage due to: (1) decreased role of combustible H2, H2S, carbohydrates, hydrocarbons and H-containing
functional groups; and (2) lower volatility and reactivity ([14]
and references therein).
3.3.5.2. Oxygen, nitrogen and sulphur. The higher contents of O, N
and S in algae compared to the terrestrial biomass (Tables 4 and
68, and Fig. 2) are significant disadvantages during algae thermochemical conversion.
The increased O concentrations cause: (1) reduced energy
value; (2) less predictable behaviour of highly oxygenfunctionalized carbohydrates; and (3) greater volatility, inorganic
vapours, smoking and soot formation. On the other hand, significant concentrations of O in algae may occur as highly reactive
forms such as COOH, OCH3 and OH functional groups ([14]
and references therein).
The high content of N in algae contributes to increase NOX and
ammonia (HN3) emissions, acid precipitation, ozone pollution,
photochemical smog and corrosion problems. Therefore, the concentration of N (together with S, Cl, some trace elements, plus
dioxins and furans) in algae and their products needs to be regulated within fairly stringent limits to maintain an acceptable feedstock quality. The NOX emissions may decrease by: (1) emission
reduction techniques such as staged combustion and injection of
NO destroying species such as ammonia, urea or hydrocarbon radicals in the furnace; and (2) algae blending with other solid fuels
poor in N ([14] and references therein).
The high content of S in algae contributes for: (1) greater SOX
emissions, smoke type smog and acid precipitation; (2) increased

19

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

generation of fine particulates and less stable and mobile sulphates; and (3) deposit formation, agglomeration, slagging and
corrosion. However, the alkaline and alkaline-earth compounds
in algae and AA are effective capture agents of S in newly formed
sulphates during algae combustion [14].
3.3.5.3. Silicon. The higher content of Si in algae (especially for diatoms) in comparison with the terrestrial biomass (Tables 4 and 6
8) is a disadvantage because it causes more erosionabrasion and
slagging problems during processing of algae and AA [14]. It should
be noted that diatom algae are about 13133 times more abundant
in Si than other algae [30]. The high contents of hard (harder than
the steels and refractory materials), coarser-grained and angular
mineral particles of some silica minerals (quartz, cristobalite, and
tridymite), feldspars, other silicates and glass in algae and AA can
be a reason for increased wear of the metal equipment surfaces.
Additionally, the high Si contents contribute to an increased formation of low-temperature alkaline silicates and glass, as well as fine
and respirable crystalline silica minerals (especially cristobalite) in
AA that can present slagging and health risks, respectively ([10]
and references therein).
3.3.5.4. Alkaline-earth elements. The higher content of alkalineearth elements (Ca plus Mg) in algae in comparison with the terrestrial biomass (Tables 4 and 68) is a big benefit during algae
and AA processing due to: (1) reduction of some technological
and environmental problems; (2) soil amendment and fertilization; (3) production of construction materials, adsorbents and
ceramics; (4) synthesis of minerals; (5) recovery of valuable components; and (6) multicomponent utilization of AA [14].
Proportions of alkaline-earth elements in biomass (including
algae) 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 [9]. These organic and inor-

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
(according to [8] and present data), 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. 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
(according to [8] and present data), wt.%.

ganic CaMg-containing phases in biomass form active and semiactive newly formed CaMg minerals and phases in BA such as
limeportlandite, periclasebrucite, anhydritebassanitegypsum
and some silicates, carbonates, phosphates and chlorides. These
newly formed reactive products bind the pozzolanic (glass) and
inert phases (mostly silicates and char) relatively quickly and cause
hardening and binder effects in the system during evaporation of
water [12,70]. The above-mentioned complex processes play a
leading role in the production of construction materials and some
other applications, and the bulk chemical and phase-mineral composition of BAs provides vital information for that purpose. Therefore, BAs were classified to phase-mineral types and sub-types
with dominant pozzolanic, inert or active properties for their different innovative and sustainable utilization [10,12]. This classification shows that AA belongs to the pozzolanic ash type (Fig. 7).
The reason for increased capture of some volatile hazardous air
pollutant elements in BAs is caused mostly by some Ca- and Mgbearing 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 [14]. The increased capture and immobilization 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 [9,10,12], which is probably also valid
to some AAs. Hence, there are potential possibilities for reduction
of harmful emissions by modification of the feed fuel composition
through tailored and self-cleaning fuel mixtures during co-firing or
co-gasification of algae with other biomasses and fossil fuels [3,9].
The data also indicate that the biomass energy can be not only
carbonneutral, but also with some extra carbon-capture and storage potential due to fixation and immobilization of CO2 in the combustion residues. For example, the mineral composition of BAs
(including AA) clearly shows the intensive formation of various
newly formed carbonates. These carbonates are a result of solid
gas reaction between the volatile CO2 (released from biomass or
occurring naturally in the atmosphere) and Ca and Mg oxyhydroxides formed during biomass combustion [9,10,12]. The last
phenomenon is actual extra CO2 capture and storage mechanisms.

20

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

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
A - Algae

Fig. 3. Mean structural organic composition of the biomass groups and sub-groups
based on 94 biomass varieties (according to [9] and present data), 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
classification system of biomass ash (based on [3,8] and present data), wt.%.

%
60

Terrestrial
biomass

50
40
30
20
10
0
Marine
macroalgae

%
60
50
40
30
20
10
0

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
classification system of inorganic matter in biomass (based on [9] and present data),
wt.%.

Amorphous matter

Oxyhydroxides

Crystalline matter

Phosphates

Carbonates

Sulphates

Silicates

Chlorides

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


classes in 7 terrestrial biomass ashes (from wood chips, corn cobs, plum pits, rice
husks, switchgrass, sunflower shells and walnut shells) and marine macroalgae ash
produced at 500, 700, 900, 1100, 1300 and 1500 C (based on [12] and present data),
wt.%.

Biomass fuels with higher Ca and Mg contents exhibit more


manageable slagging, fouling and corrosion problems ([14] and references therein). Additionally, these fuels could produce suitable
bed materials that may reduce the need to use additives in
fluidized-bed combustion chambers [14]. Such type of combustion

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Fig. 7. Positions of 8 biomass ashes in the phase-mineral classification of biomass


ashes. The data are based on mean contents of amorphous matter, silicates and
other mineral classes (carbonates + oxyhydroxides + phosphates + sulphates + chlorides) for biomass ashes produced at 500, 700, 900, 1100, 1300 and 1500 C (based
on [12]), wt.%. Abbreviations: BC, beech wood chips; CC, corn cobs; MM, marine
macroalgae; PP, plum pits; RH, rice husks; SG, switchgrass; SS, sunflower shells;
WS, walnut shells.

requires additional use of carbonates, quartz or other silicates as a


bed material. Hence, algae highly enriched in Ca, Mg and silica may
reduce such a need.
Various CaMg minerals in BA (including AA) like Ca silicate
hydrate gel, Ca aluminosilicate hydrate, portlandite, calcite and
ettringite can be formed in the ash disposals (under high pH) and
such crystallizations may reduce mobility either by physically
reducing the porosity of the ash or by chemically binding the elements [10,71]. On the other hand, the high contents of alkalineearth and alkaline oxides in ash may cause burning damage on
human and plant tissues [71].

3.3.5.5. Alkaline and halogen elements. The higher contents of alkaline and halogen elements (Br, Cl, F, I, K, Na, Li, and excluding Cs
and Rb) with unfavourable modes of occurrences (organic matter,
chlorides, sulphates, carbonates, oxalates, nitrates and some oxyhydroxides, phosphates and amorphous material) in algae compared to the terrestrial biomass (Tables 4 and 68) are among
the most technological and environmental challenges during thermochemical conversion of algae. They can cause: (1) increased
volatilization and formation of many dangerous components (Cl2,
HCl, HBr, HF, dioxins, furans, TEs, others); (2) enhanced fine particulate emissions; (3) greater quantity of water-soluble fraction; (4)
generation of low-melting 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 AA; (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 gasifiers; and (10) burning damage on human
and plant tissues by alkaline oxides in AA ([14] and references
therein). The technological countermeasures may include fuel
selection and blending, fuel pre-treatment (mostly water washing)
and application of appropriate additives, temperature and ash
cleaning systems. For example, the industrial algae washing to

21

remove water-soluble phases prior to use of algae as fuel 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 [14]. Additionally, the variable phase and
chemical composition of biomass fuels gives the possibility of
reducing high contents of alkaline and halogen elements and
improving the algae performance by modification of the feedstock
composition through tailored fuel mixtures with other biomasses
and fossil fuels [12].
On the other hand, the high contents of alkaline and halogen
elements can have some positive effects during algae conversion.
For instance, some alkaline inorganic constituents (like KCl, NaCl
and others) can act as catalysts or catalyst precursors for thermochemical conversion of algae. The high alkali and Cl contents in
algae 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. Moreover, the alkaline BAs like AA 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. Finally, Br and Cl enriched biofuels as algae
(typical for K-LA inorganic sub-type in Fig. 4) could also play
the role of self-cleaning fuels for the successful capture and
immobilization of Hg ([14] and references therein). The use of such
advanced approaches is of particular interest for algae because the
improved and/or cleaner fuel blends may contribute for reducing
or avoiding many technological or environmental problems during
thermochemical conversion of algae.
3.3.5.6. Trace elements. The higher contents of many trace elements
(TEs) in algae in comparison with the terrestrial biomass (Tables 4
and 8) are among the most serious disadvantages during algae conversion. Trace elements contribute to potentially more environmental problems related to their emissions and formation of
dangerous components during algae conversion [14]. 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 [13]. These challenges are
also valid to algae and AA even to a higher extend because they
contain increased concentrations of many toxic and potentially
toxic TEs such as Ag, As, Be, Cd, Cl, Co, Cr, F, Ni, Pb, Sb, Se, Sn, Th,
U, V and Zn with unfavourable modes of occurrences.
Certain modes of element occurrence in fuel favour their mobility (leaching and volatilization) during processing. For example, it
was found that TEs in biomass and BA (including algae and AA)
tend to occur in much more mobile and hazardous compounds
than in coal and coal ash because they associate preferably with
the easily decomposed organic matter and water-soluble minerals
and phases ([14] and see Section 3.3.6). Additionally, TEs such as
As, Br, Cd, Cr, Hg, Pb, Sb, Se, V and Zn demonstrate the highest
volatilization potential during biomass combustion [14]. The same
TEs plus Ba, Co, Cu, Li, Mn, Mo, Ni, and Sr show significant watersoluble occurrence in biomass and BA [14]. For instance, the
volatilization behaviour of 11 TEs (As, Be, Co, Cu, Mn, Ni, Pb, Sb,
Se, V, and Zn) during thermal conversion (combustion, pyrolysis
and gasification) of algae, as well as their water leaching behaviour
from algae have been studied [60]. As a result, the high volatility of
As, Pb, Sb, Se and Zn, and minor volatility of Be, Co, Cu, Mn, Ni and
V was found during algae conversion, while all of the tested TEs,

22

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

except for Be and Pb, were partially leached from the algae [60]. It
can be seen that most of the observations for biomass are also valid
to algae; however, this topic is still at initial stage of investigations.
Hence, some dangerous, volatilized and water-soluble elements
might cause some environmental pollution of the air, water
(surface and subsoil water), soil, flora and fauna with possible subsequent penetration into the food chain during algae and AA
utilization.
The concentration of hazardous TEs (plus Cl, N and S) in algae
and AA needs to be regulated within fairly stringent limits to maintain an acceptable quality and highly efficient separation of these
elements in power plants using algae. On the other hand, the
highly variable composition of biomass (including algae) gives
the possibility of reducing the harmful emissions by modification
of the feed fuel composition through tailored fuel mixtures. As
mentioned above some biofuels can be to some extent
self-cleaning fuels because a number of their original constituents and their newly formed minerals and phases are active
during thermochemical conversion and can play more or less a
capture and immobilization 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 specific surface area [12]. Unfortunately,
algae are also highly enriched in Cl and S and the formation of less
stable chlorides and sulphates in AA strongly diminished their selfcleaning potential for TEs. On the other hand, the high concentrations and modes of occurrence of some TEs (As, Cd, Au, B, Be, Br, Cl,
Cr, Ga, Ge, I, La, Li, Lu, Sc, Se, Sr, Ta, Ti, Th, others) may have a
resource recovery potential for certain algae and AAs and an economical assessment is required in such cases. However, this topic
is still at initial stage of investigations.
3.3.6. Water-soluble fraction, extractives, pH and electrical
conductivity
The positive correlations between water-soluble fraction,
extractives, pH and electrical conductivity, and their higher values
in comparison with the terrestrial biomass are characteristic features of algae and have mostly disadvantages for their processing.
The water-soluble fraction (total mineralisation or dissolved
solids) of terrestrial biomasses varies between 0.3% and 7.8%
(mean 2.2%) [9], while this fraction in algae is 15.1% (Table 7). On
the other hand, the quantity of water-soluble fraction of coal
(0.28.4%, mean 2.1% [9]) is comparable to that of terrestrial biomass, but much lower than that of algae. These leachates mainly
consist of inorganic and, to lesser extent, organic components
and their high contents in algae are a very serious disadvantage
during thermochemical conversion (see below). The total mineralisation of leachates is mostly salty and sea salty for terrestrial biomass, while algae shows brine character according to the
classification of natural waters ([9] and references therein). As
expected, this characteristic correlates positively and significantly
with electrical conductivity, inorganic matter and mobile S, Cl,
Na and N components in biomass [9]. The decreasing order (based
on mean values) of water-soluble elements leached from various
terrestrial biomasses is: Cl > K > Na > P > S > N > Mg > Mn > Al >
Ca > Fe > Si plus some As, Ba, Co, Cu, Mo, Pb, Sr, Ti, V and Zn ([9]
and references therein). It was also found that elements such as
As, Cd, Co, Ga, Lu, Pr, Sr, U and V plus Al-, Cl-, Mg-, N-, Na-,
O- and S-containing phases correlate positively with the watersoluble fraction in some biomasses (including algae), which is
abundant in chlorides, sulphates, oxalates and nitrates plus some
carbonates and amorphous material [13]. It was stated that most
of the mobile elements (As, Br, Cd, Cl, Cr, Hg, K, Na, Pb, S, Sb, Se,
V and Zn) associate preferably with organic matter and

water-soluble minerals and phases in biomass [9,13]. The above


order and trends are probably similar to those of algae; however,
future investigations in this very interesting topic are required.
For example, the mobilization behaviour of TEs (As, Be, Co, Cu,
Mn, Ni, Pb, Sb, Se, V, and Zn) during water leaching of algae has
been studied. All of the tested TEs, except for Be and Pb, were partially leached from algae [60]. The high water solubility of elements such as Cl, K, Na, S, Sr and Zn from algae was also
identified [38,53]. The above results show that the water-soluble
fraction play a very important role for algae because it can be
abundant in water-soluble macronutrient and micronutrient elements (B, Ca, Cl, Cu, H, K, Mg, Mn, Mo, N, O, P, S, Zn, others), as well
as in many hazardous elements [14].
On the other hand, the content of water-soluble fraction in BAs
is normally high, namely 3.945.1% (mean 27.0%), while the same
value for coal ashes is much less (0.27.2%, mean 1.6%) [14]. This
value for AA is 42.8% (Table 7) and it is close to the maximum
for BAs. The decreasing order (based on mean values) of watersoluble elements leached from various terrestrial BAs is:
Cl > S > K > Na > Sr > Ni > Mn > Cd > Cr > Zn > Co > Si > Mo > Li >
(Mg, Pb) > Ca > Cu > Ba > P > Se > Sb > Al > Fe > (Br, Hg) > (As, B, Sn,
Ti, V) ([3] and references therein). The mobilization behaviour of
TEs (As, Be, Co, Cu, Mn, Ni, Pb, Sb, Se, V, and Zn) during water leaching of products from algae conversion (combustion, pyrolysis and
gasification) has also been studied. It was found that V was significantly leachable from the combustion residue, while the other TEs
were generally less leachable from the thermal conversion residues. These TEs are significantly less leachable from residues prepared under pyrolysis and gasification conditions than from
residues prepared under combustion conditions [60]. It was also
found that TEs such as B, Cr, Li, Mo, Ni, Pb, Rb, Sr, U, V, Y and Zn plus
ash-forming Ca-, Cl-, Fe-, K-, Mg-, Na-, P- and S-containing phases
correlate positively with the water-soluble fraction of some BAs
(including AA) [13]. These observations are a strong indication that
the nutrients and some potentially hazardous TEs can associate
preferentially with the water-soluble fraction of BAs. The above
orders and trends are probably also valid for that of AA; however,
future investigations in this topic are also required. The data show
that the water-soluble phases in BAs mostly include phases of
alkali and alkaline earth elements such as: (1) highly soluble chlorides (sylvite, halite), sulphates (arcanite, syngenite, ettringite,
gypsum), oxides (lime), hydroxides (portlandite), nitrates, carbonates and bicarbonates; and (2) certain less soluble carbonates (calcite), phosphates (phosphorites, apatite) and silicates (Ca silicates,
feldspars) [3]. Many of them are characteristic minerals and phases
of AA (see Section 3.5). It is interesting to note that the yield of
water-soluble fraction from AA (42.8%) increases to 43.1% and
47.2% after 24 h and one week room storage, respectively, and after
that this yield remains almost unchanged. This observation confirmed the intensive hydration, hydroxylation and carbonation of
the water soluble minerals by moisture and CO2 in the air through
storage of AA even for a short period of time. The above results also
show that significant portions of the above listed water-soluble
nutrient elements in algae and AA 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. However, the future large-scale algae and AA applications 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;

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Fig. 8. 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 fluid temperatures (based on [12]), C. Abbreviations: A,
algae biomass; AVB, all varieties of biomass; B, bituminous coal; C, coal; CB,
contaminated biomass; DT, initial deformation temperature; FT, fluid temperature;
HAB, herbaceous and agricultural biomass; HAF, herbaceous and agricultural fibres;
HAG, herbaceous and agricultural grasses and flowers; 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.

(9) ash swelling and obstructing soil pores ([14] and references
therein). 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 specific plant
nutrients in a relatively short amount of time [10]. On the other
hand, the combination of high bulk concentrations and elevated
water leaching behaviour of some valuable and easily recoverable
elements in algae and AA could have significant industrial potential due to their effective and low-cost recovery, as well as for synthesis of new materials [10,14].
The electrical conductivity in the water-soluble leachates from
terrestrial biomasses normally varies between 0.7 and 3.5 mS cm 1
[9], while this leachate from algae reveals the maximum value of
19.8 mS cm 1 (Table 7), which is in accordance with the total mineralisation [9]. It was found that the electrical conductivity correlates positively and significantly with water-soluble fraction,
inorganic matter, pH, cellulose and mobile S, Cl, Na and N components in biomass [9]. It is well known, that the conductivity of
water solutions is highly dependent mostly on the concentration
of dissolved salts. Hence, the algae leachate has higher ionic
strength than the terrestrial biomass leachates, while the latter
ones are relatively more salt-free solutions (with small charge
imbalances) [9].
The pH of leachates from water extraction procedures of terrestrial biomasses is normally between 5.1 and 6.7 [9], while the pH of
this leachate from algae is 6.8 (Table 7). Thus, the solutions are
mostly slightly acidic for terrestrial biomasses, while algae show
neutral character due to their composition. It was found that pH
correlates positively and significantly with inorganic matter and
mobile S, Cl and Na components in biomass [9]. For comparison,
the pH values for coal are typically more variable (2.27.5, mean
5.9) due to the highly changeable proportions of Fe sulphides,
organic acids and carbonate concentrations [9]. The relatively
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. As a
result, different elements in biomass tend to be mobile and they
are prone to pose environmental concerns ([10,13] and references

23

therein). On the other hand, the high pH of terrestrial BAs (8.112.9


[13]) and AA (8.4 in Table 7) 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 mobilization 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 ([14] 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 ([14] and references therein). Unfortunately, prolonged leaching during AA weathering in disposal sites
could provoke a decrease of pH and significant release of many
TEs from AA [14]. Hence, future investigations in this very important issue are also required for algae and AA.
The bulk extractives are not an integral part of the biomass
structure and they consist of various organic (mostly carbohydrates, proteins, hydrocarbons, oils, aromatics, lipids, fats, starches,
phenols, and waxes) and inorganic salt components extracted individually or sequentially by different polar or non-polar solvents
from biomass, but commonly water, ethanol, benzene and toluene
and their mixtures ([9] and references therein). The bulk extractives (Table 6) play an important role for algae because their contents in this fuel are 0.517.2% (mean 7.5%), while the bulk
extractives in the common terrestrial biomass such as wood and
woody biomass and some herbaceous and agricultural biomass
(shells, husks, pits and other residues) are normally lower [9].
The high content of extractives in algae 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 water-soluble fraction and extractable inorganic
matter [14].

Fig. 9. Areas of low (<1100 C), medium (11001300 C) and high (>1300 C) initial
deformation (DT) ash fusion temperatures for 55 biomass varieties in the chemical
classification system of biomass ash (based on [12]), wt.%.

24

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

3.3.7. Ash-fusion temperatures


The lower ash-fusion temperatures (AFTs) of algae (Table 6 and
Fig. 8) in comparison with most terrestrial biomasses [12] are a
very serious disadvantage during algae thermochemical conversion [14]. It is widely accepted that the severe deposit formation,
slagging and fouling problems during biomass combustion result
from the low ash-melting temperatures [14]. Some indicative
trends of biomass in comparison with coal were identified recently,
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; and (2) lower values of Al, Fe, N, S, Si, Ti, inorganic matter,
oxyhydroxides, silicates and sulphatessulphides [9]. Hence, such
differences are reasons for the lower AFTs of biomass in comparison with coal. 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 [12]. The above listed biomass trends are particularly valid
for algae and it seems that the latter fuel is among the worst cases
for slagging and fouling [12]. For example, the fusion characteristics of three seaweeds have been studied [45]. It was found that
they have low ash-fusion temperatures and easy slag formation.
The initial melting was observed at 600815 C and the reason
for that was related to the high contents of alkali chlorides in the
fuel [45]. Additionally, different particle alterations with increasing
temperature were observed microscopically in BAs [3]. It was identified that these alterations for AA occur at the lowest temperature
ranges in comparison with the terrestrial biomass. For instance, the
AA particles shows: (1) fragmentation with some initial and local
agglomeration (500 C); (2) significant agglomeration with initial
melting (700 C); (3) extensive agglomeration with significant
melting (900 C); (4) extensive melting (1100 C); and (5) complete
melting between 1100 and 1300 C. Therefore, a selection of optimal temperatures for thermochemical conversion (up to 750
800 C) is required to avoid the above problems (see Section 3.6).
Another possibility is the preliminary algae washing to eliminate
the abundant water-soluble components in them which contribute
greatly for lower AFTs. Furthermore, a beneficial approach for
problematic low ash-fusion algae or alternative bed materials for
fluidized bed combustion is to use various additives, namely
kaolinite, mullite, bentonite, K feldspar, plagioclase, olivine, quartz,
lime, Al minerals, hematite, carbonates, peat, coal, coal ash and
others ([12] and references therein). The application of such additives is to prevent the agglomeration, sintering and slagging tendencies by achieving higher ash-melting temperatures. The above
blending is to provoke the intensive formation of more refractory
minerals (silica minerals, mullite, and Ca and Mg silicates and oxides) and less fluxing phases (K and Na silicates, chlorides, sulphates and phosphates) in the system [12]. However, there are
many solid fuels which are naturally abundant in refractory minerals and appropriate blending of such fuels can avoid the use of
expensive algae pre-treatment procedures and non-fuel additives
[12]. For example, the favourable or less problematic future fuel
mixtures between algae, terrestrial biomass, coal and other solid
fuels may include an adjustment of chemical and phase composition for fuel blends to fit preferentially some chemical ash types
and sub-types (Fig. 9 and [12]). Hence, the fuel mix can play a leading role to solve different technological and ecological problems
related to algae thermochemical conversion.
3.4. Phase and mineral composition of algae
Algae are photosynthetic organisms with simple growing
requirements (light, sugars, CO2, N, P, and K) that produce commonly organic components such as proteins, carbohydrates, lipids

and nucleic acid, and, to a lesser extent other organics (pigments,


enzymes, antioxidants, fatty acids, and vitamins A and C), plus
inorganic components (alkali minerals) in large amounts over
short periods of time [2,5,1618,23,25,27,46]. Algae consist of cells
and the intercellular water is fixed by this network structure, while
the soft walls consist mainly of complex carbohydrates and proteins [47,61]. Algae are significantly different from terrestrial
plants in terms of their chemical composition, as well as physiological, structural and morphological features [44,56]. However, the
biochemical composition of green algae is similar to land plants
[56]. This composition of algae biomass can be changed by varying
the growth and nutritional parameters and thus inducing richness
of targeted biomolecular fractions (mainly lipids and carbohydrates) in resultant biomass steering to the purpose of cultivation
[21,23]. Algae constitute a unique feedstock due to the high levels
of proteins, lipids and carbohydrates (sugars) and none of the other
biomass feedstocks and biofuel technologies currently available on
the market offers similar advantages for both biodiesel and ethanol
production [28].
It was identified (see Section 3.2) that the algae biomass in
comparison with the terrestrial biomass normally has: (1) higher
values of inorganic matter, hemicellulose, proteins, lipids and
nucleic acids; and (2) lower values of organic matter, carbohydrates, cellulose, cellulose crystallinity index and lignin.
3.4.1. Organic matter
Algae have much lower organic matter content than the terrestrial biomass (see Section 3.3.2). The organic composition of aquatic biomass is variable (Table 6) and different in comparison with
the terrestrial biomass [9]. The organic constituents of algae normally include: proteins > carbohydrates > lipids > nucleic acid;
while the structural components are: hemicellulose > cellulose > lignin (Table 6 and Fig. 3). Nevertheless, there are cases
among algae varieties where the above orders for certain components are changeable. It was also identified that most TEs together
with C, Ca, Fe, H, K, Mn, P and Ti (and their bearing phases) correlate positively with organic matter of some biomasses (including
algae) [13], but additional investigations are required for algae.
3.4.1.1. Carbohydrates. One of the main components in algae is the
carbohydrates fraction [16,44] and some of the most productive
algae contain large amounts of these saccharides [17]. Their bulk
contents (Table 6) in algae are highly variable (4.083.6%, mean
29.9%, organic basis). Macroalgae are commonly more enriched
in carbohydrates compared to microalgae [23,61]. Additionally,
microalgae have high contents of starch [56], while macroalgae,
except green algae; do not have such high concentrations
[23,56]. Algae contain various carbohydrates which are distinctively different from those of terrestrial plants [23,56]. Carbohydrates also differ in quality and quantity according to algae
species; however, the decreasing order of their bulk contents are
normally: red algae > brown algae > green algae [23,56]. The concentration of stored carbohydrates has seasonal variations and
they reach the maximum value in autumn [22]. Due to the carbohydrate difference, terrestrial biomass-based technology cannot be
directly applied to algal biomass [56]. Carbohydrates are good candidates for biofuel production such as biogas, bioethanol and
biooils [22].
3.4.1.2. Structural organic components. The contents of hemicellulose, cellulose and lignin in algae are highly variable (Table 6).
Hemicellulose is the predominant carbohydrate in algae species
(Fig. 3), while cellulose is the principal carbohydrate in higher
plants [57].
Crystalline, paracrystalline and amorphous celluloses with different contents were identified in biomass [35]. It was found that

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

all native crystalline celluloses are composites of two distinct


phases (Ia and Ib) due to the multiple crystal forms in them
[32,33]. The form Ia is triclinic and dominant in bacterial and algal
celluloses (lower plants); whereas the other form Ib is monoclinic,
more stable and dominant in celluloses from higher plants [32,33].
It was also identified that the calculated Segal crystallinity index of
cellulose [35] is relatively low for algae in comparison with the terrestrial biomass [9]. Cellulose in terrestrial biomasses shows significant negative correlations with lignin, Na and N [9]. Most TEs such
as Ag, As, Au, Ba, Be, Cd, Co, Cr, Cs, Ga, Ge, Mo, Ni, Pb, Rb, Sb, Sc, Se,
Ta, W, Zn and rare earth elements (Dy, Er, Eu, Gd, Ho, Lu, Sm, Tb,
Tm and Yb, excluding only the light La, Ce, Pr and Nd) together
with C-, Fe-, K-, Mg-, Mn-, O-, P- and Si-bearing phases correlate
positively with cellulose for some biomasses (including algae)
[13]. These observations are also valid to algae; however, additional investigations are required.
Hemicellulose has a random and amorphous structure and this
carbohydrate in terrestrial biomasses shows: (1) significant positive correlations with S, Si and ash yield; and (2) significant negative correlations with lignin and Ca. The positive correlations of
hemicellulose with inorganic matter and Si, plus highly mobile elements in terrestrial biomass such as S, Cl, N and K, strongly indicate
the abundance of authigenic opal, sulphates, chlorides and nitrates
in the hemicellulose matrix [9]. It was found that hemicellulose is
the structural component with the fewest positive correlations
with TEs, excluding As, Cd, Co, Ga, Sr, U and V plus Al-, Cl-, Mg-,
N-, Na-, O- and S-containing phases for some biomasses (including
algae) [13]. These observations are also valid to algae; however,
additional investigations are required.
Algae normally do not contain lignin [23,44] or contain quite
limited amount of this component [5,40,56,57] especially in red
algae and certain green algae [5]. Lignin contents are lower in
the aquatic biomass and particularly in marine algae as compared
to the terrestrial ones [57]. For example, the typical maximum
position of the large peak (broad diffusion reflection) for lignin in
the terrestrial biomasses was not observed for algae studied by
XRD [9]. Since the roles of hydrophobic lignin are mostly to provide
mechanical strength to the cell walls and to conduct water without
its leaking from the cell walls, such properties are mostly important for terrestrial plants, but not for aquatic plants and algae
[57]. Algae almost do not include lignin because they do not need
to stand rigidly in the water, while this constituent is needed for
the rigidity of terrestrial plants. Thus, the cell wall of algae is structurally flexible and this biomass can provide many technological
benefits for biofuel production [56]. Additionally, the ash yields
normally increase with decreasing lignin contents in biomass
[72] and this is typical of algae (Tables 6 and 7). Finally, the correlation analysis shows that lignin in terrestrial biomasses has: (1)
significant positive relationships with Na and Mg; and (2) significant negative associations with cellulose, hemicellulose and S [9].
It was also found that lignin correlates positively with B, Bi, Cu,
Hf, Li, Nb, Pb, rare earth elements (Ce, Dy, Ho, La, Nd, Pr, Sm, Tb,
Yb and excluding Er, Eu, Gd, Lu, Tm), Sn, Th, W, Y, Zn and Zr plus
Al-, C-, Ca-, H-, P- and Ti-bearing phases for some biomasses
(including algae) [13]. These observations are also valid to algae;
however, additional investigations are required.
Each variety of biomass can be better suited to specific pretreatment and conversion processes depending upon its structural
composition [14]. For example, the high contents of cellulose and
hemicellulose in biomass can be leading features for considering
suitable processing technologies due to: (1) increased reactivity,
hydrophilicity, hydrolysis, oxidation, volatility, crystallinity, sugar
and inorganic matter; and (2) decreased calorific value, aromaticity, density and char yield. On the other hand, the high contents
of lignin in biomass can be leading features for considering suitable
processing technologies due to: (1) increased calorific value,

25

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
([14] and references therein). Therefore, the structural composition
of biomass varieties among biomass groups and sub-groups were
specified 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 [9]). It can be seen
(Fig. 3) that algae belong to the uncommon HCL structural type
and this provoke more specific pre-treatment and conversion
processes.
3.4.1.3. Lipids, proteins and other organic components. Lipids
(triglycerides, oils) are typical of animal biomass and are also contained in vegetable biomass (oilseed crops) and algae [59]. The
organic composition of algae normally includes high contents of
lipids [16,17,27] as these concentrations (organic basis) are highly
variable (0.977.0%, mean 23.4%, Table 6). The heterotrophic algal
cells demonstrate much higher yields of total lipids and neutral
lipids than the photoautotrophic cells [20]. Macroalgae, except
green algae, commonly do not have high contents of lipids (up to
5%) [23,56]. In contrast, microalgae have greater concentrations
of lipids in comparison with macroalgae [4,6,20,23,25,27,56,61]
as the former algae are able to develop even 5086% of lipid contents within their cells depending on species and under specific
cultivation conditions [6,21,25,61]. However, it was also found that
some of the most productive microalgae are depleted in lipids [17].
The genetic manipulation of microalgae to improve lipid content
has also been noted. For example, massive accumulation of lipids
in microalgae typically occurs in stressed environment and under
these conditions (nutrient limitation and high light intensity) the
growth rate of cultures are greatly reduced [6]. It was also identified that the high accumulation of lipids in the microalgae cells is
caused by nutrient stress such as N or P limitation [51]. Lipids
accumulated in algae cells can be extracted and converted into biodiesel by means of transesterification [5] and such a transportation
fuel produced from microalgae lipids has 80% average energy content of petroleum [61].
Proteins are essential nutrients for humans and animals and
they are typical of animal biomass and are also contained in vegetable biomass (oilseed crops) and algae [59]. Algae are able to
develop high contents of proteins within their cells depending on
species [25,31,61]. The concentrations of proteins in algae (organic
basis) are highly variable (6.071.0%, mean 42.8% Table 6). Microalgae are normally more enriched in proteins than macroalgae
[16,17,23,27,56]. The organic composition of algae also includes
nucleic acids [16] and uronic acids [31]. The concentrations of
nucleic acids in algae (organic basis) are up to a few percents
(1.06.0%, mean 3.9% Table 6). The contents of uronic acids are
more variable (124%) [31] and these acids constituent alginate
(a major polysaccharide of alginic acid composed of three different
uronic acids), which is used mostly in textile and food industries,
as well as for therapeutical use [53,56]. Alginate is enriched in
Ca, Sr, Ba and Mg because it has high affinity to these divalent
cations [56].
3.4.2. Inorganic matter
Algae have much higher inorganic matter content than the terrestrial biomass (see Section 3.3.2). The XRD data and microscopic
investigations of marine macroalgae show the trace occurrence of
opal, calcite, halite and amorphous inorganic material, while the
dry water-soluble residue leached from them reveals the presence
of halite, sylvite and amorphous inorganic material, and traces of
magnesite and arcanite (Fig. 10 and [9]). Hence, inorganic species

26

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

Fig. 10. XRD patterns of marine macroalgae (MM), dry water-soluble residue (DWR) from MM and high-temperature ashes (HTAs) of MM generated at 500 C/2 h, 700 C/1 h,
900 C/1 h, 1100 C/1 h and 1300 C/1 h (based on [11]). Abbreviations: A, anhydrite (CaSO4); Cc, calcite (CaCO3); Cps, counts per second; Ha, halite (NaCl); IAM, inorganic
amorphous material (non-glass and glass); L, lime (CaO); MFe, magnesite rich in Fe ((Mg,Fe)CO3); Mu, mullite (Al6Si2O13); OM, organic matter; Op, opal (SiO2nH2O); Pl,
plagioclases (NaAlSi3O8CaAl2Si2O8); Port, portlandite (Ca(OH)2); Q, quartz (SiO2); Sy, sylvite (KCl). The occurrence of Q, Mu and Pl in the sample MM-HTA-1300 is a result of
contamination from the broken ceramic crucible.

from chloride, sulphate, carbonate and silicate mineral classes


were identified in algae [9]. It was found that TEs such as Ag, As,
Cd, Co, Er, Lu, Sr, Tm, U and V plus Al-, Cl-, Mg-, N-, Na-, O-,
S- and Si-containing phases correlate positively with inorganic
matter of some biomasses (including algae) [13]; however, many
more elements were also identified to be enriched in algae
compared to the terrestrial biomass due to the high inorganic matter in the former fuel (see Sections 3.2 and 3.3.5.6).
3.4.2.1. Sulphates. Sulphates are typical mineral class of algae in
contrast to the terrestrial biomass and the minerals from this class
are highly mobile species [9]. It is well known that halophytes
(formed in saline environment) compensate for water relation
problems in the saline environment by accumulating salts, so that
water can move into the plant. Similarly, marine algae actively
absorb such salts. Ion ratios are often specific to particular families
or species, and most flowering plants accumulate more Na than K.
However, different species within a genus may respond differently
with respect to ions accumulation: K > Na > Cl > S; Na > K > Cl > S;
Na > K > S > Cl, and thus salts are absorbed or excreted by the algae
according to need [38]. It can be seen that this order is

K > Na > Cl > S for marine and freshwater algae (Table 6) and
S > Na > Cl > K for the marine macroalgae sample studied (Table 7).
Arcanite identified in algae (Fig. 10) can be authigenic and especially epigenetic in origin mostly due to the evaporation and precipitation of highly mineralised water solutions in algae during
their drying [9]. For example, arcanite was identified in the dry
water-soluble residue leached from algae (Fig. 10). Other
alkaline-earth and alkaline sulphates (especially gypsum) probably
also occurs in algae due to the high contents of S, K, Na, Ca and Mg
(Tables 6 and 7), but the detection limit of XRD is low for biomass
and additional methods are required for their identifications
[73,74]. For instance, certain Ca, K and Ba sulphates with unclear
origin were also found in some terrestrial biomass enriched in such
elements [9].
3.4.2.2. Chlorides. Chlorides, similar to sulphates, are characteristic
mineral class of algae in contrast to the terrestrial biomass and the
minerals from this class are highly mobile species. Halite and sylvite were identified in algae (Fig. 10) and they can also be authigenic and especially epigenetic in origin mostly due to the
evaporation and precipitation of water during algae drying, similar

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

to sulphates [9]. For example, traces of halite were observed in


algae, whereas both halite and sylvite were found in the dry
water-soluble residue leached from algae (Fig. 10). Chlorides of
Na, K, Ca and Bi with unclear origin were also identified in some
terrestrial biomass enriched in such elements [9].
3.4.2.3. Carbonates. Carbonates identified in algae include calcite
and magnesite (Fig. 10) and this mineral class is normally less
abundant in comparison with the terrestrial biomass. These minerals are relatively less mobile species and can be detrital and authigenic in origin [9]. For instance, the detrital carbonate occurrence
in the algae feedstock is a result of contamination by some shell
remains. On the other hand, the carbonates can also be authigenic
and especially epigenetic in origin mostly due to the evaporation
and precipitation of water during algae drying, similar to sulphates
and chlorides. Calcite and dolomite were also found in some terrestrial biomass [9].
3.4.2.4. Silicates. Silicates have one of the most complex origins
among other mineral classes in biomass. For example, different silicates (quartz, cristobalite, feldspars, pyroxenes, olivines, zeolites,
clay and mica minerals) with detrital, authigenic and technogenic
origin were identified repeatedly in terrestrial biomass [9].
Silicates can be both detrital and authigenic species in algae [9].
Traces of opal, quartz and amorphous silica were identified microscopically or by XRD in algae (Fig. 10). The detrital silicates, especially quartz, can be a result of contamination by sand particles
fixed on plant surfaces in the algae feedstock. Additionally, some
detrital and finely dispersed sand grains (commonly <1 lm) can
also be introduced into the plant by water suspensions through
endocytose process during algae growing [9]. In contrast, opal
can have authigenic (syngenetic and epigenetic) origin in algae.
Silica minerals in biomass are a very interesting case due to their
different nature in biomass ([9] and references therein). Shortly,
the authigenic silica occurs by absorption of silicic acid from the
mineralised solutions and their precipitation in plants. These solutions flocculate in cell structures, deposit between and within plant
cells and undergo polymerisation. As a result organically deposited
silica hydrate (opal) is formed, which is dominantly in an amorphous state and occasionally in crystalline forms. Such silica formations in plants are also described in the literature as
phytoliths. Opal was found as spicules of fresh-water sponges
and in the cell wall or the lumen of the epidermis for some plants.
Individual small (12 lm) silica particles, a distinct pure silica shell
layers, as well as silica inclusions that were embedded in the
organic matrix were also observed in other plants. Similar silica
occurrences are probably also characteristic of algae, especially
diatoms because their cellulose walls are composed of polymerized
and hydrated silica [21]. Additionally, the silicon distribution is
highly dependent on the plant species. For instance, grasses and
straws contain a high amount of silica for the plants rigidness to
maintain its posture. Similarly, silica in wood occurs mainly in supportive tissues such as bark ([9] and references therein). Hence, silica also plays a role similar to structural component in some plant
tissues because it forms a rigid microstructure that gives structural
stability of plants (including algae). It should be stated that a similar silicification process is also well known for some coals. It represents initial formation of opal and its subsequent dehydration
and recrystallization to cryptocrystalline chalcedony and later to
more stable low-temperature quartz and cristobalite in/on cell
walls [9].
3.5. Phase and mineral composition of algae ash
The XRD data of ashes generated from AA at 5001300 C show
the occurrence (mean contents) of inorganic classes: amorphous

27

matter > crystalline


matter > sulphates > chlorides > oxyhydroxides > carbonates > silicates (Table 10 and Figs. 6 and 10). These
classes include the inorganic species: glass > anhydrite > halite >
portlandite > calcite > sylvite > quartz > lime
(Table
10
and
Fig. 10). The formation and transformation of specific phases and
minerals in AA with increasing temperatures can also be seen
(Table 10 and Fig. 10). The mineral composition of three seaweed
ashes produced at 530 and 600 C has been studied [45]. The minerals and phases identified in these ashes include chlorides such as
sylvite and halite, crystalline silica phases and some alkaline-earth,
alkaline and Al silicates.
3.5.1. Inorganic amorphous matter
The newly formed glass, amorphous (non-glass) materials and
poorly crystallized structures of inorganic matter in AA are represented by maximums of amorphous halo in the range of 1540
(for CuKa radiation) on the base line of the XRD patterns (Fig. 10
and [11]). It should be stated that this inorganic amorphous matter
consists mostly of glass above 700 C, and, to a lesser extent, some
non-glass and poorly crystallized materials generated at 500 and
700 C. The glass formation increases with increasing temperatures, especially above 900 C (Table 10 and Fig. 10). The microscopic investigations show that the first melt portions appear in
AA produced between 500 and 700 C, while the complete AA
melting occurs between 1100 and 1300 C. The glass content in
AA is one of the highest compared to some terrestrial biomass
ashes generated at the maximum temperatures (Fig. 6 and [11]).
Hence, the AA composition contributes for enhanced production
of: (1) low-temperature melt with increasing temperature; and
(2) low-temperature glass during melt cooling. The extremely
low ash-fusion temperatures are typical of algae (Table 6, Fig. 8
and Section 3.3.7).
3.5.2. Silicates
Silicates in AA are represented by quartz that can be both primary and secondary in origin. This silicate can be new-formed
mineral in AA as a result of amorphous silica crystallization and
opal recrystallization up to 500 C. Quartz can also be original mineral in AA due to the possible presence of unaltered sand relics.
Quartz is stable up to 900 C in AA and after that this mineral is dissolved in the melt (Table 10 and Fig. 10).
3.5.3. Oxides and hydroxides
Oxides and hydroxides in AA are newly formed minerals and
represented by secondary lime and tertiary portlandite. The latter
mineral is mostly formed from lime hydroxylation by air moisture
through ash storage (see Sections 3.3.6 and 3.5.5). The secondary
lime is generated from the decomposition and oxidation of organically bound Ca and calcite during algae combustion. It can be seen
that the lime formation is very intensive at 500, 700 and 900 C
during organic matter combustion and calcite decomposition and
after that this mineral is dissolved in the melt or takes part in
the formation of anhydrite due to lime sulphation up to 1100 C
(Table 10 and Fig. 10).
3.5.4. Sulphates
Sulphates in AA are represented by newly formed anhydrite
generated from the reaction between lime and sulphur oxide gases
produced from the combustion of organic matter and calcite
decomposition. Anhydrite is stable between 500 and 1100 C and
the most intensive formation of this secondary mineral is between
900 and 1100 C (Table 10 and Fig. 10) as a result of lime sulphation. Anhydrite is dissolved in the melt between 1100 and
1300 C. It is interesting to note that anhydrite and lime are the
only minerals stable at 1100 C and the initial melt formed in AA
is not enough for their complete dissolution at this temperature

28

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

(a)

HCL organic type


K inorganic type
K-LA inorganic sub-type

(b)

BAs [3,11,12] and coal ashes [75,76]. The main differences are
related to the melt formation at lower temperatures and more
intensive generation of chlorides and sulphates in AA in comparison with other BAs and coal ashes.
It was identified that AA has dominant pozzolanic-active properties based on the phase-mineral composition and these peculiarities are important for the advanced AA utilization (Fig. 7 and [12]).
It was also found that most TEs (mainly lithophile, noble and
radioactive elements plus As, Cd, Ga, Ge, Pb, Sb, Sc, Se, Sn, V and
Zn) together with ash-forming Al, Cl, Fe, Mg, Na, S, Si and Ti correlate positively with inorganic amorphous matter and silicates in
some BAs (including AA). A significant number of TEs also associate
with phosphates (B, Ba, Bi, Ce, Co, Cs, Cu, Ga, Hf, La, Li, Nb, Nd, Pb, Pr,
Sn, Th, U, Zn, Zr) and carbonates, oxides and hydroxides (B, Ba, Bi,
Co, Cs, Cu, Ga, Hf, Li, Pb, Rb, Sn, Sr, Y, Yb) in these BAs. In contrast,
relatively few TEs correlate positively with sulphates (Co, Cr, Cu,
Mo, Ni, Rb, Sr, U, V) and chlorides (B, Co, Sr, U, V), which are typically
water-soluble phases in these BAs. The association of TEs with different mineral classes confirmed most of the relationships found
between TEs and major and minor elements in the above BAs
[13]. These observations are also valid to AA; however, future
detailed investigations are required in this important topic.
3.6. Behaviour of algae during combustion

Fig. 11. DTA and TGA profiles in air of: (a) marine macroalgae (MM); and (b) hightemperature ash (HTA) of MM generated at 500 C/2 h (based on [11]).

(Table 10 and Fig. 10). Some primary sulphates may also occur in
AA because traces of such minerals were identified in algae (see
Section 3.4.2.1).
3.5.5. Carbonates
Carbonates in AA are represented by calcite and this mineral
can be primary (original), secondary and tertiary in origin. For
example, some original calcite can occur in AA up to 700900 C
because algae contain this mineral as shell relics. However, calcite
is mostly secondary in origin as a result of reaction between lime
and CO2 gases generated from the combustion of organic matter
at 500 C, and, to a lesser extent at 700 C (Table 10 and Fig. 10).
Some calcite can also be tertiary in origin as a result of lime
hydroxylation and subsequent portlandite carbonation by moisture and CO2 in air through ash storage.
3.5.6. Chlorides
Chlorides in AA are represented by halite and sylvite and these
minerals can be both primary and secondary in origin. For example, some original halite and sylvite relics can occur in AA because
algae contain these minerals. However, the above chlorides are
mostly secondary in origin as a result of reaction between alkaline
elements and Cl gases generated from the combustion of organic
matter. It can be seen that the most intensive formation of chlorides in AA is at 500 and 700 C and some of them can occur even
at 900 C (Table 10 and Fig. 10).
It should be stated that the above listed phase-mineral transformations in AA are similar to these described in detail for terrestrial

The DTATGA profiles in air of different biomasses show very


similar combustion behaviour for organic matter despite their
highly variable contents of structural components [11]. The DTA
profiles for these biomasses reveal that the organic matter oxidation is characterized by large exothermic effects mostly between
200 and 650 C and represented as two consecutive peaks with
maximums at 324351 C and 425520 C. The two major exothermic reactions are accompanied by two intensive mass losses
according to TGA curves [11]. The exothermic maximums for algae
are at 334 and 520 C and they are accompanied by mass losses of
organic matter including one major stage between 200 and 600 C
with two sub-stages at 200400 C and 400600 C (Fig. 11(a)). It
should be emphasized that algae also have an additional third
and small exothermic peak with maximum at 782 C and accompanied by some weight loss (Fig. 11(a)) and this interesting observation is described below.
It was found that both major exothermic temperatures for
organic matter do not correlate definitely to the contents, distribution and decomposition/oxidation stages of specific structural
components in different biomasses [11]. The results demonstrate
that these two consecutive exothermic peaks are simply due to
the two stage combustion behaviour of organic matter, namely
(1) devolatilization and burning of combustible volatile matter;
and subsequently (2) char formation and combustion; simultaneously from the three structural components of the bulk organic
matter [11]. The above observations are not in accordance with
widely accepted statements in literature about the organic matter
decomposition. For example, the reference data reveal the following decomposition temperature ranges: (1) 150350 C for hemicellulose; (2) 240500 C for cellulose; and (3) 160900 C for
lignin ([11] and references therein). It was also accepted that the
combustion and pyrolysis behaviour for the organic matter of algae
is characterized by: (1) hemicellulose decomposition and initial
stage of degradation of cellulose (200270 C); (2) degradation of
lignin and final cellulose decomposition (270370 C); plus decomposition of carbohydrates (180270 C) and proteins (320450 C)
[44]. It was also found that a wide range of furan derivatives is
observed in algae combustion and pyrolysis products, which are
more numerous than those from terrestrial biomass [44].
The two consecutive exothermic peaks for different biomasses
have changeable heights as the first peak is dominantly lower in

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

height. The height ratios between the first and second peak indicates the reactivity of biomass and it was found that algae show
the lowest reactivity (Fig. 11(a)) in comparison with the terrestrial
biomasses [11].
In contrast to different biomasses, the DTATGA profiles of their
BAs produced at 500 C show very distinct and complex transformation behaviour due to their highly variable inorganic composition [11]. These profiles for AA reveal: (1) loss of adsorbed water
associated with the endothermic effect at 96 C; (2) burning of
the residual char related to the exothermic effects mainly between
300 and 800 C; (3) calcite and probably portlandite decomposition
corresponding to the endothermic reaction at 538 C; (4) melting
of chlorides revealed by the endothermic reaction at 745 C; and
(5) anhydrite decomposition above 1100 C; accompanied by some
mass losses (Fig. 11(b)). The lime formation from calcite, chlorides
melting and anhydrite decomposition for AA are also supported by
XRD data (Fig. 10 and Table 10). DTATGA profiles of biomasses
and their BAs can also specify some important ash-melting temperatures (hemispherical and mostly fluid temperatures) represented by endothermic reactions involving no change in mass or
with limited mass loss [11]. The temperature related to the fluid
state of AA is observed at about 1240 C following the anhydrite
decomposition (Fig. 11(a) and (b)).
As mentioned above, algae has an additional third and small
exothermic peak between 740 and 830 C (maximum at 782 C)
accompanied by some mass loss (Fig. 11(a)) and this peak is characteristic only for algae in contrast to the terrestrial biomasses
[11]. Therefore, further investigations were conducted and it was
found that this phenomenon is related to oxidation of capsulated
residual char. A few individual char particles were recognised by
light microscopy in the algae ashes obtained at 500 and 700 C.
These black particles show signs of original algae textures and
structures and they are encapsulated by coarse sized chloride
aggregates built up of cubic crystals. The AA is highly enriched in
Cl, Na and K represented by halite and sylvite (Tables 7 and 10).
It is well known that the melting points of these minerals are in
the temperature interval 770801 C [11]. Therefore, the endothermic peak at 745 C (with some mass loss) seen on DTATGA profiles for AA produced at 500 C (Fig. 11(b)) is consistent with
eutectic melting of a halitesylvite mixture and this is supported
by XRD data (Fig. 10 and Table 10). The DTATGA profiles of AA
(Fig. 11(b)) also show exothermic effects: (1) at 307 and 603 C
accompanied by some mass losses related to the burning of some
residual char particles; and (2) at 792 C followed by intensive
mass loss due to oxidation of unburned and encapsulated char.
Hence, the combustion of the encapsulated residual char after
782 C (Fig. 11(a)) and 792 C (Fig. 11(b)) follows closely melting
of the chloride matrix at 745 C because the chloride melt allows
oxygen diffusion and combustion of this unburned char. Reference
investigations also identified some char oxidation at higher temperatures (600900 C) only for lignin derived char from lignin rich
biomass varieties ([11] and references therein). However, this is
not the case herein because marine macroalgae normally do not
contain lignin [44] or contain quite limited amount of this component [40]. Additionally, it was found that the existence of two
major biomass char combustion stages (with two exothermic
peaks) was not related to the occurrence of two specific types of
chars with a different nature because any structure evolution of
the char was not found [77]. Finally, the above combustion mechanism for the residual char encapsulated in chlorides can also be
valid for char entrapped by certain carbonates, sulphates, phosphates and silicates [11].
The combustion temperature has a leading effect on the ash
content and qualitative and quantitative composition of ash produced from biomass ([11] and Fig. 10). For example, the study of
different biomasses reveals that the ash yields determined at

29

11001500 C are 759% lower than those produced at 500 C, as


algae shows the maximum mass loss [11]. It was found that the
increased losses are typical for biomass varieties abundant in Ca,
Cl, K, Mg, Na, P, S, chlorides, sulphates, carbonates and phosphates
[12] and this is characteristic of algae. In contrast, minimum losses
occur for biomass varieties highly or significantly enriched in Si, Al,
Fe, Ti, amorphous matter and silicates [12]. These weight losses for
biomasses (including algae) are normally higher than for coals and
such differences are a result of some more intensive phase transformations (loss of adsorbed and combined water, combustion of
volatile matter, decomposition of less stable minerals) and higher
volatilization behaviour of certain mobile elements (Br, C, Cl, H,
Hg, K, N, Se, S and other TEs) from biomass phases in the higher
temperature ranges ([3] and references therein). As a result of
algae combustion, intensive volatilization of elements occurs in
the temperature range between 200 and 800 C from: (1) organic
matter forming elements (C, H, N, O); and (2) inorganic elements
associated with organic matter (mainly K, Na, Cl, S, Ca, Mg, P and
TEs); as covalently or ionically bound elements, organic-metal
components, adsorbed ions or metal ions in ion-exchanged forms
bound to specific functional groups. Elements such as C, Ca, Cl, K,
Mg, Na, S and many TEs contained in less stable inorganic matter
such as carbonates (>500 C), chlorides (>750 C) and sulphates
(>1100 C) can also be released during decomposition and/or melting of such minerals. The volatilized elements can: (1) escape the
system as volatile components; (2) form discrete inorganic phases
in ash; (3) react with each other; and (4) react with original or
newly formed inorganic matter of algae and AA [11]. Hence, selection of optimal temperatures for thermochemical conversion (up to
750800 C) is required to avoid some of the above problems (see
also Section 3.3.7). A confirmation of the last statement is a study
on the volatilization behaviour of 11 TEs during thermal conversion (combustion, pyrolysis and gasification) of algae [60]. It was
found high volatility of Se (7997%) and As (5179%) below
500 C, while elements such as Pb, Sb and Zn were mainly volatilized above 700 C. The volatility of these elements increased sharply to more than 90% with increasing temperature from 700 to
1100 C. The volatility of Be, Co, Cu, Mn, Ni and V was relatively
minor below 1100 C [60].
The systematization of physico-chemical processes during algae
combustion (Figs. 10 and 11, and Table 10) shows that the original
organic and inorganic matter in algae undergoes: (1) moisture
evaporation (90100 C); (2) devolatilization of organic matter
and burning of combustible gases (200400 C); (3) char formation
and burning (400800 C); (4) formation of intermediate and less
stable hydroxides (200600 C), carbonates (200700 C), inorganic amorphous (non-glass) material (200700 C) and chlorides
(200800 C); (5) crystallization of more stable silicates (200
900 C), sulphates (2001100 C) and oxides (2001100 C); and
(6) melting accompanied by dissolution of the refractory minerals
(7001200 C); with increasing combustion temperatures in the
system. Then, there is formation of glass and limited crystallization
of melt accompanied by some salt condensation and hydroxylation, hydration and carbonation of newly formed phases during
cooling of AA. Finally, some post-combustion transformations of
the newly formed minerals and phases to stable species during
weathering among hydroxides, sulphates, carbonates and chlorides can also occur due to their hydration, hydroxylation and carbonation by moisture and CO2 in the air through storage of AA.
3.7. Major technological and environmental challenges related to
algae-based fuels
The present data demonstrate that the high contents of inorganic matter with unfavourable modes of element occurrences
(chlorides, sulphates, carbonates, oxalates, nitrates and some

30

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

%
60
50
40
30
20
10
0

S type

%
60
50
40
30
20
10
0

C type

%
60
50
40
30
20
10
0

K type

%
60
50
40
30
20
10
0

CK type

Four types

%
60
50
40
30
20
10
0
Amorphous matter
Crystalline matter

Oxyhydroxides
Phosphates

Carbonates
Silicates

Sulphates
Chlorides

Fig. 12. Mean distribution of amorphous matter, crystalline matter and mineral
classes in biomass ash types based on 8 biomass ashes of rice husks and switchgrass
(S type), beech wood chips (C type), corn cobs, marine macroalgae and
sunflower shells (K type), and plum pits and walnut shells (CK type) produced
at 500, 700, 900, 1100, 1300 and 1500 C (based on [12]), wt.%.

oxyhydroxides, phosphates and amorphous material) in algae and


AA provoke the most important technological and environmental
challenges during algae processing for biofuel application and
especially their thermochemical conversion. As described above
they can cause: increased volatilization and formation of many
dangerous components; enhanced fine particulate emissions;
greater quantity of water-soluble fraction; low ash-fusion temperatures; high amount of active melts with low viscosity; increased
deposit formation, fouling, agglomeration, slagging and corrosion;
enhanced deleterious effects in construction materials incorporating AA; and health problems. Additional technological and environmental challenges related to algae use include: relatively high
values of moisture, bulk density, alkaline and halogen elements,
O, N, S, Si, and many trace elements including hazardous ones;

and relatively low values of volatile matter, reactivity and calorific


value compared to the terrestrial biomass. The present data confirmed some previous investigations that the algae chemistry and
properties restrict the use of this fuel for direct combustion and
gasification and the digestion method seems to be the most suitable conversion technology for algae [44]. The last statement is
in a disagreement to other opinions emphasizing that the thermochemical conversion provides significant advantages (simplicity,
shorter conversion time, higher productivity and compatibility)
in comparison with the biochemical conversion of algae [25].
The genetic inorganic types in terrestrial biomasses and their
BAs have a leading importance for technological and environmental problems, similar to coals and coal ashes [14]. This statement is
also valid to algae and AA. Shortly, certain major associations
related to the occurrence, content and origin of inorganic matter
in the terrestrial biomass system were identified and they include:
(1) SiAlFeNaTi; (2) CaMgMn; and (3) KPSCl (plus N)
(Figs. 2, 4, 5 and 9). It should be noted that Na in algae changes
its position and belongs to the association (3) of the most mobile
elements. The above associations were applied for classification
of inorganic matter in biomass (Fig. 4) and BA (Figs. 5 and 12) 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 classification and indicator purposes connected with innovative and sustainable processing of biomass and
BA. For example, the concept of dividing inorganic matter into
detrital and authigenic categories of biomass (Fig. 4), and original
(primary) or newly formed secondary and tertiary classes of BA
(Figs. 5 and 12) 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 (watersoluble) and reactive, and with low decomposition or melting temperatures during biomass processing. The latter case is typical for
AAs because they belong to K type and K-LA sub-type (Figs. 4,
5, 9 and 12). Therefore, inorganic matter types, mineral classes and
groups and specific mineral species are likely to be the major reasons for many problems during biomass processing (similar to
coal). 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 defluidization and
composition of residues during biomass processing. The detrital
minerals can be important for enhanced abrasionerosion (hard
and angular quartz, feldspars, rutile, corundum), formation of some
low-temperature eutectics, partitioning element behaviour and for
decreasing combustion efficiency and increasing operating costs
for the handling of inert materials during biomass processing.
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 flotation can be difficult during biomass upgrading.
In contrast, detrital minerals in biomass occur as physically more
easily separable particles similar to coal. Hence, many of the key
constraints in the efficient thermal treatment of biomass may arise
mostly from authigenic minerals which are characteristic of algae.
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 organic
matter and these organically associated elements and their
phases react during the thermal treatment of biomass and appear

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

dominantly as newly formed inorganic matter in residues. This


case is also typical of algae. 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
specific impacts on the different technological and environmental
problems related to the advanced and sustainable use of biomass
including algae.
It was highlighted that the utilization of biomass resources will
be one of the most important factors for environmental protection
in the 21st century [78]. Therefore, another crucial challenge for
large-scale production of algae biofuels and biochemicals is the
availability of sustainable algae resources. It is well known that
the natural biomass is a renewable energy source, while biofuel
is still an incomplete renewable energy resource at present
because the modern bioenergy chains are usually associated with
additional use of fossil fuels when considering the complete biomass life cycle assessment ([14] and references therein). Furthermore, the biofuel demands should not compete with food and
feed production.
The conversion of algae sources from natural water ecosystems
(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. Shortly, not enough knowledge is available to truly comprehend the importance of the natural water ecosystems and given
this lack of knowledge humans should be very careful not to further disturb and destroy these native systems [14]. Natural water
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. For
example, there is balance of mobile elements (mostly nutrients)
between the algae species and their habitats when considering
algae regeneration. The algae harvesting from natural ecosystems
can reduce significantly the nutrient capital and balance of the
water ecosystem because large amounts of the most mobile nutrients can be exported. Hence, the above case cannot be a sustainable approach because the large-scale use of such algae
resources will cause further disturbances and imbalances in the
already stressed natural water ecosystems. These observations
lead to the conclusion that exploitation of natural water ecosystems should remain undisturbed to a maximum extent in order
to avoid adverse impacts. In the current trend towards largescale production of fuel and energy from algae resources it would
thus be desirable to restrict the exploitation of natural ecosystems
and instead derive the algae from a limited number of feedstocks.
The above reasons strongly indicate that the potential favourable
algae resources for biofuel production, despite some possible technological and contamination problems, should be focused (in
decreasing order of significance) preferably on aquatic phytomass
such as:
(1) Non-edible natural algae, but grown only in existing extra
population and/or eutrophication zones of rivers, lakes, seas
and oceans.
(2) Specifically cultivated non-edible algae plantations grown in
freshwater, seawater and waste water within open or closed
ponds and photo-bioreactors.
For example, it was stated that a removal of macroalgae from
some extrapopulation zones in the Baltic Sea is a way to diminish
the content of main nutrients (N, P and K) in the sea water and thus
counteract eutrophication as the algae contain high concentrations
of these nutrients [53].
Therefore, the potential algae resources for biofuel and biochemical production should always be divided initially into sus-

31

tainable and unsustainable management resources under strictly


specified environmental criteria. The complete algae life cycle
assessment is very important tool for that purpose. 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, production (phytoplankton chlorophyll a concentration),
estimation, monitoring, planning, control and policy implementations of sustainable algae feedstock ([14] and references therein).
The above criteria might very-well reduce the overall available
and sustainable algae resources. Therefore, it may be speculated
that the huge contribution of algae in the future energy mix is significantly overestimated if appropriate additional measures and
corrections are not taken into considerations regarding the availability and management of unsustainable and unfavourable algae
resources for production of biofuels. Still, algae could play an
important role as a fuel and energy resource when combined with
other efforts, namely terrestrial biomasses, other types of
renewable energy and overall reducing the fuel and energy
consumption.

4. Conclusions
Algae-based fuels are considered to be the most sustainable,
renewable, effective and environment friendly response to climate
change and foodfeed security, as well as the only renewable
energy resource that has the capacity to meet the global demand
for fuels in the long-term. The initial step related to algae use as
fuel includes two fundamental aspects, namely: to extend and
improve the basic knowledge on composition and properties;
and to apply this knowledge for the most advanced and sustainable
utilization of algae. Therefore, certain conclusions about the composition and properties of algae and algae ash, as well as some
advantages, disadvantages and challenges connected with algae
biofuel application can be made:
(1) The major advantages related to the composition and properties of algae biomass normally include: (1) higher values of
alkaline-earth elements, extractives, hemicellulose, lipids,
nucleic acids, pH and proteins; (2) lower values of C, initial
ignition temperature and lignin; and (3) less variable composition and properties; compared to the terrestrial biomass.
On the other hand, the benefits of algae biomass in comparison with coal are commonly: (1) higher values of alkalineearth and nutrient elements, reactivity and volatile matter;
and (2) lower values of initial ignition and combustion
temperatures, C, S, and many trace elements including
hazardous ones.
(2) The major disadvantages connected with the composition
and properties of algae biomass normally comprise: (1)
higher values of alkaline and halogen elements, ash (inorganic matter), bulk density, chlorides, combustion temperature, electrical conductivity, inorganic amorphous matter,
moisture, oxyhydroxides, silicates, sulphates, water-soluble
fraction, N, O, S, Si and many trace elements including hazardous ones; and (2) lower values of ash-fusion temperatures, carbohydrates, cellulose, cellulose crystallinity index,
heating value, organic matter, reactivity, volatile matter
and H; compared to the terrestrial biomass. On the other
hand, the obstacles of algae biomass in comparison with coal
are commonly: (1) higher values of alkaline and halogen elements, ash, moisture, N, O and some hazardous trace elements; and (2) lower values of ash-fusion temperatures,
bulk density, heating value and H.

32

S.V. Vassilev, C.G. Vassileva / Fuel 181 (2016) 133

(3) It was identified that the genetic inorganic types in algae


(detrital and authigenic) and algae ash (primary, secondary
and tertiary) have a leading importance for technological
and environmental problems, similar to the terrestrial biomasses, coals and their ashes.
(4) The systematization of physico-chemical processes during
algae combustion shows that the original organic and inorganic matter in algae undergoes: (1) moisture evaporation
(90100 C); (2) devolatilization of organic matter and burning of combustible gases (200400 C); (3) char formation
and burning (400800 C); (4) formation of intermediate
and less stable hydroxides (200600 C), carbonates
(200700 C), inorganic amorphous (non-glass) material
(200700 C) and chlorides (200800 C); (5) crystallization
of
more
stable
silicates
(200900 C),
sulphates
(2001100 C) and oxides (2001100 C); and (6) melting
accompanied by dissolution of the refractory minerals
(7001200 C); with increasing combustion temperatures
in the system. Then, there is formation of glass and limited
crystallization of melt accompanied by some salt condensation and hydroxylation, hydration and carbonation of newly
formed phases during cooling of algae ash. Finally, some
post-combustion transformations of the newly formed minerals and phases to stable species during weathering among
hydroxides, sulphates, carbonates and chlorides can also
occur due to their hydration, hydroxylation and carbonation
by moisture and CO2 in the air through storage of algae ash.
(5) The high contents of inorganic matter with unfavourable
modes of element occurrences (chlorides, sulphates, carbonates, oxalates, nitrates and some oxyhydroxides, phosphates
and amorphous material) in algae and algae ash provoke the
most important technological and environmental challenges
during algae processing for biofuel application and especially their thermochemical conversion. They can cause:
increased volatilization and formation of many dangerous
components; enhanced fine particulate emissions; greater
quantity of water-soluble fraction; low ash-fusion temperatures; high amount of active melts with low viscosity;
increased deposit formation, fouling, agglomeration,
slagging and corrosion; enhanced deleterious effects in construction materials incorporating algae ash; and health
problems.
(6) The unfavourable composition and properties of algae
restrict their use for direct combustion and gasification
and the digestion method seems to be more suitable conversion technology for algae. A selection of optimal temperatures (up to 750800 C) and appropriate pre-treatment,
upgrading or blending procedures are required to avoid the
technological and environmental problems during direct
thermochemical conversion of algae.
(7) The indefinite availability of sustainable algae resources for
production of biofuels is a very important obstacle because
the conversion of algae sources from natural ecosystems into
energy resources may lead to serious environmental problems. The exploitation of native water ecosystems should
remain undisturbed to a maximum extent as resources for
algae production in order to avoid adverse impacts. Therefore, the potential favourable algae resources for biofuel production, despite some possible technological and
contamination problems, should be focused preferably on
aquatic phytomass such as: (1) non-edible natural algae,
but grown only in existing extra population and/or eutrophication zones of rivers, lakes, seas and oceans; and (2) specifically cultivated non-edible algae plantations grown in
freshwater, seawater and waste water within open or closed
ponds and photo-bioreactors. The potential algae resources

for biofuel and biochemical production should always be


divided initially into sustainable and unsustainable management resources under strictly specified environmental
criteria.
(8) It was found that the disadvantages of algae for biofuel and
biochemical applications prevail significantly over the
advantages; however, the major economic, environmental
and social benefits appear to compensate the technological
and other barriers caused by the unfavourable composition
and properties of algae.

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