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Chapter

Recent Advances in
Thermochemical Conversion
of Biomass
Meegalla R. Chandraratne and Asfaw G. Daful

Abstract

The chapter focuses on recent trends of biomass conversion into valuable

energy, chemicals, gaseous and liquid fuels. Biomass is presently the largest source
of renewable energy and the primary bioenergy resource in the world. A com-
prehensive discussion on different types, sources and compositions of biomass is
presented. The most abundant biomass on the earth is lignocellulose and it rep-
resents a major carbon source for chemical compounds and biofuels. The chapter
presents a thorough review of lignocellulosic biomass and the importance of
biomass as a renewable source. It then reviews biomass classification and composi-
tion. It introduces the analysis of biomass feedstock. Biomass is converted to energy,
chemicals and clean fuels using various conversion techniques such as thermochem-
ical, chemical and biochemical. The chapter provides a thorough examination of
thermochemical conversion processes that use high temperatures to break down the
bonds of organic matter. It briefly introduces combustion and gasification, followed
by a comprehensive review of different pyrolysis techniques.

Keywords: bioenergy, hydrothermal processing, lignocellulosic biomass,

biomass composition, pyrolysis, gasification, combustion

1. Introduction

Due to industrialization, population growth, and urbanization, there has been a

rapid increase in global energy demand and consumption over the past few decades.
Currently, more than 80% of the world energy demand is supplied by fossil fuels.
Global attention on alternative resources has increased due to the high prices and
limited reserves of fossil fuels, environmental pollution and climate change. As
a result, there is renewed interest in the production and use of renewable energy
resources such as biomass, solar, wind, geothermal and tidal. However, biomass
is the only renewable energy resource to produce transport fuels. Various biomass
components, including sugars, starches and lignocellulosic materials can be used
to produce transport fuels and potentially limit the use of fossil fuels. On the other
hand, biomass residues and wastes (such as agricultural residue, food waste, animal
manure, municipal solid waste) as resources for bioenergy production are promis-
ing alternatives to reduce environmental issues concerning waste management and
disposal. If improperly managed, these residues and wastes could lead to greenhouse
gas emissions, pests breeding, insects, foul odor, etc. Converting these residues and

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Recent Perspectives in Pyrolysis Research

wastes, that would otherwise have been left to decompose, into useful bioenergy is
environmentally beneficial for waste management as well as to reduce the depen-
dence on fossil fuel [1–3]. Lignocellulosic biomass (LCB) such as agricultural crop
residues, wood and forestry residues are readily available, inexpensive and promis-
ing resource for biofuels. Biomass can be considered as the best option for meeting
future energy demand sustainably. The efficient utilization of biomass resources is
essential by having more efficient biomass production and conversion [4].
Biomass is an organic matter of plant or animal origin that is living or was
living in the recent past [5]. Biomass is perhaps the oldest source of energy used
by humans. People have used biomass as an energy source for cooking, heating,
and lighting for thousands of years. The energy contained in biomass originally
came from the sun. Plants get their energy from the sun and convert water (H2O)
and carbon dioxide (CO2) into oxygen (O2) and sugars (carbohydrates) in the
process of photosynthesis. The energy of sunlight is stored in chemical bonds
of plant organic matter. When different conversion processes break the bonds
between adjacent carbon, hydrogen and oxygen molecules of carbohydrates, these
substances release their stored chemical energy [6]. Biomass is a renewable energy
source as it can be produced year after year and, therefore, is valuable as a fuel
source. Compared to petroleum-based products, the use of biomass represents the
potential to reduce CO2 emissions, resulting in negligible or zero SOX emissions
and lower NOX emissions [7, 8].
Biomasses include agricultural crop residues, forestry and wood residues, pur-
posely grown bioenergy crops, aquatic biomass, sewage sludge, digestate, animal,
industrial, municipal and food waste. Various types of wastes such as cow manure,
poultry litter, wastepaper, sewage sludge, municipal and many industrial wastes
are treated as biomass because these are a mixture of organic (and non-organic)
compounds.

2. Importance of biomass

Non-renewable sources produce a significant portion of current energy supplies

globally and their use is associated with the emission of CO2 into the atmosphere.
However, about 10–15% of this demand is covered by renewable resources, making
biomass by far the most important renewable energy source used to date. Biomass
contributes to 9% - 13% of the total energy supplies in industrialized countries.
However, biomass energy is the primary energy source in many developing nations,
contributing to about 20–30% of the total energy supplies. In some developing
countries, biomass covers 50 to 90% of the total energy demand. In industrial-
ized countries, biomass is used as a modern bioenergy source for industrial (heat,
electricity), transportation (biofuels) and domestic (mainly heat) applications
[9–11]. A significant part of the traditional use of biomass (firewood, sometimes
animal waste) in developing countries is non-commercial and used for cooking
and heating, generally by the poorer part of the population. The non-commercial
use of biomass is poorly mapped and as a result, the contribution of biomass to the
energy supply is not accurately known [12]. Solid biomass is one of the primary
energy sources (mainly used for cooking) in many developing countries, especially
in rural sub-Saharan Africa and South Asia. Traditional biomass use is not sustain-
able because it may result in soil quality degradation by depriving soil nutrients and
burning it in inefficient cooking stoves can cause high levels of indoor air pollution.
Most households in sub-Saharan Africa rely on the traditional use of biomass to
meet their daily cooking needs. In countries such as the Democratic Republic of
Congo, Ethiopia, Tanzania, Nepal and Nigeria, more than 80% of the total energy

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Recent Advances in Thermochemical Conversion of Biomass
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demand is met through biomass energy sources. In developing countries, biomass is

used to some extent in industries such as brick manufacturing [13, 14].
Crude oil is an excellent source of energy, it is easily transported and energy-
rich, it is one of the most energy-dense fuels. The energy density of crude oil and
methane are 42 MJ/kg and 55 MJ/kg, respectively. Even coal has a good energy
density (27–32 MJ/kg). Compared to these fossil fuels, the energy density of
biomass ranges from 8 MJ/kg for greenwood to 20 MJ/kg for dry plant matter.
Biomass has low bulk density and causes a major problem during storage, handling
and transportation for further processing. The bulk density of biomass varies from
around 40 kg/m3 for loose straw and bagasse, in the range of 80–100 kg/m3 for
agricultural residues and 150–200 kg/m3 for woody biomass to the highest levels of
around 250 kg/m3 for some wood residues. This translates to needing more biomass
to produce for the same amount of heat or power and higher transportation costs,
processing costs, etc. [15, 16].
Most of the biomass used today is derived from agricultural and forestry
biomass. Agricultural biomass includes the food-based portion and the non-food-
based portion of crops. The food-based portion comprises oils and simple carbo-
hydrates of crops such as corn, sugarcane and beet. The non-food-based portion
comprises complex carbohydrates of crops such as the leaves, stalks, seed hulls,
orchard trimmings, nutshells, rice husk, bagasse, coffee pulp and straw. Forestry
biomass includes wood residues associated with the production of timber in the
forest, as well as the processing of timber into their final products [17, 18].
The comparatively low energy density of biomass means that issues associated
with land use must be taken into consideration. Expansion of land use for biomass
production can lead to a high potential for environmental damage due to deforesta-
tion, erosion, nutrient runoff, emissions, etc. This reduces any potential benefit
of using biomass. Large-scale cultivation of non-food perennial energy crops for
bioenergy feedstock is feasible when sufficient land areas are available. The best
land for agriculture must be used to grow food crops. To avoid food versus energy
conflict, it is important to use infertile/marginal lands for energy crop cultivation
with little use of fertilizer or pesticides and potentially needing minimal water.
Energy crops should not be grown at the expense of biodiversity [15]. For produc-
tive agricultural systems, prospects of biomass production based on the factors
provided by nature such as light, soil, water and nutrients with soil and water are
considered as the most crucial natural resource constraints. Identifying land areas
with minimal disturbance to food production is critical for technically and eco-
nomically feasible biomass production. To achieve sustainable large-scale biomass
production, marginal or abandoned agricultural land has been widely considered
as important. Energy crops are adaptive to marginal or abandoned agricultural
land. Compared with food crops, energy crops such as switchgrass and miscanthus
generally require much less water to grow and are suitable to partially replace the
dryland crops [19]. Beyond the vast areas of land needed to grow energy crops, the
long-term impact of soil quality due to repeated removal of biomass is a concern.
Water usage is another major concern. Biomass may have a moderate carbon foot-
print, but its water footprint is enormous. Only a small percentage of the biomass
produced by photosynthesis is currently being cultivated, harvested and used, but
how much can be used sustainably? As with any approach to energy generation, the
massive demand for energy stresses the need to be careful in considering the use of
biomass for energy generation [15].
Plants grow through photosynthesis by absorbing atmospheric CO2 and produc-
ing carbohydrates that form the building blocks of biomass. Water and sunlight are
the other two key ingredients of photosynthesis, which typically convert less than
1% of the energy available in sunlight to chemical energy. When biomass burns,

3
Recent Perspectives in Pyrolysis Research

it releases CO2 back to the atmosphere that the plants had absorbed recently. i.e., the
burning of biomass does not add to the total CO2 inventory of the earth. Therefore,
biomass is considered the most important source of green carbon or carbon-neutral
fuel. In order to decide the true carbon neutrality, the overall biomass chain needs to
be considered, including cultivation (for energy crops), harvesting, drying, stor-
age, transportation and processing. These represent a significant cost, energy needs
and CO2 emissions sources [7]. All these factors must be taken into consideration
in life-cycle analysis for sustainability. Biomass plays an integral part in the overall
sustainable energy solution, but it is not a panacea. Biomass for biochar production
makes land usage more complex. The effect is not only the land usage for biomass
supply but also the impacts of adding biochar to soils. The impacts may include
increased productivity and, hence, reducing the land area required for food produc-
tion as well as the potential for biochar to make previously unmanaged or marginal
land economically productive, thereby facilitating the conversion of marginal land
to agriculture [15, 20].
Besides heat and electricity generation, biomass can be used as a feedstock for
biofuel production with technologies already available on the market. Biofuels are
liquid or gaseous fuels produced from biomass and can be used as a replacement or
blended with fossil-based fuels for different applications. This makes biomass very
valuable within future energy systems based on renewable/sustainable sources of
energy. The biomass potential for the energy markets needs to be evaluated without
affecting the demands for food and fodder as well as for raw materials. The use of
biomass has been debated critically on the background of the ongoing environmen-
tal and sustainability discussions.

2.1 Biomass classification

Biomass can be classified into different groups depending upon the origin where
it is produced, including agricultural biomass, forestry and wood processing resi-
dues, dedicated energy crops (crops cultivated solely for energy), aquatic biomass,
sewage sludge, digestate (remains of anaerobic digestion), industrial crops, animal,
industrial, municipal and food waste. Biomass is also classified based on the chemi-
cal composition as carbohydrates, lignin, essential oils, vegetable oils, animal fats
and natural resins (gums) [21–24].
Agricultural biomasses are natural products of all agriculture. These include a
wide range of agricultural crop residues (the non-food based portion of crops) that
are not harvested for commercial use or byproducts from harvesting or processing,
such as corn stover (leaves, stalks, husks and corn cobs left in a field after harvest),
sugarcane bagasse, straw residues (barley, oats, rice, rye, wheat) from grain pro-
duction, waste from other food crops, horticulture and food processing. Other
plant residues include husks of grains and seeds, coconut shells, fruit stones and
nut shells. Straw and other agricultural residues usually have a high ash content and
contain chlorides and potassium compounds, which can cause high levels of corro-
sion in boilers. The problems of corrosion and slagging can be mitigated by burning
biomass at lower temperatures [1, 18].
Forestry and wood processing residues include trees not harvested during
logging (trees that are not valuable as timber, such as imperfect commercial trees,
dead wood and other non-commercial trees), biomass removed during logging
(such as crowns and branches from fully-grown trees) in commercial forests, waste
from forest and wood processing (such as palm kernel shells, wood pellets, wood-
chips, leaves, barks, lumps and sawdust) as well as materials removed during forest
management operations (such as trunks of smaller trees removed during thinning,
dead and dying trees removed during forest control) [1, 25].

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Recent Advances in Thermochemical Conversion of Biomass
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Dedicated energy crops are another expanding and potentially larger source of
biomass. Energy crops are low maintenance and high yield crop species that give
the maximum energy yield. These are grown specifically for their fuel value (energy
applications) on marginal land unsuitable for agriculture. Several crops can be
readily used as energy sources. There are two types of energy crops, herbaceous
and short-rotation woody. Herbaceous energy crops include perennials that are
harvested annually after reaching maturity. It takes 2–3 years to reach complete
production. These are grasses such as switchgrass, miscanthus, bluestem, elephant
grass, bamboo and wheatgrass. They do not require replanting for 15 years or more.
The drawback with most non-woody energy crops is that their chemical proper-
ties generally make them less suitable for combustion due to the high ash and salt
content [18, 26, 27]. The woody crops are grown on short rotations, generally with
more intensive management than timber plantations. These fast-growing hardwood
trees are harvested within 5–8 years of planting. These crops include poplar, willow,
maple, cottonwood, black walnut and sweetgum [25, 27].
Different kinds of algae, plants and microbes found in water form another
class of biomass called aquatic biomass. Aquatic biomasses include macroalgae,
microalgae, seaweed, kelp, water hyacinth and aquatic plants [24]. Animal, indus-
trial, municipal and food waste and sewage sludge are other important sources of
biomass. Animal and human waste biomass includes waste resulting from farm
and processing operations, manure of different animals, cooked or uncooked food,
fruits, paper and pulps. When these waste materials are treated and converted to
useful energy products, not only energy is being produced, but the problem of
disposing of these materials is also reduced to a certain extent. Industrial waste
involves waste from various manufacturing and industrial processes like paper
sludge from paper industry, sugar cane residues from sugar mills, waste from food
processing industry, waste oils, textile industry waste and others. Animal and
human waste biomass and industrial biomass are categorized differently because
industrial biomass may contain different types of toxic chemicals and harmful
additives. In contrast, animal and human waste are primarily free of these types
of harmful materials [28]. Municipal solid waste (MSW) includes waste from
residential, commercial and industrial sectors that contains a significant amount
of biomass (such as paper, cardboard, wood, food, leather, textiles and yard trim-
mings) with energy content. Food waste contains residues from food and drinks
manufacture, preparation and processing, post-consumer waste, animal fat, used
cooking oil etc. Other biomasses include Industrial crops (crops developed to pro-
duce specific chemicals or feedstocks such as kenaf), construction and demolition
waste, building material waste, abandoned furniture etc. [18, 25].

2.2 Composition of biomass

The chemical composition of biomass is different from fossil fuels. The most
abundant biomass on the earth is LCB, including agricultural biomass, forestry
and wood processing residues, dedicated energy crops, industrial crops and food
waste, hence, the following sections primarily focus on LCB. Plant biomass is a
complex mixture of polymers consisting of three key elements: 42–47% of car-
bon (C), 40–44% of oxygen (O) and 6% of hydrogen (H), all percentages in dry
matter, whose total content generally reaches above 95% [24, 29]. Plant biomass
also contains macronutrients such as nitrogen (N), phosphorus (P), potassium
(K), magnesium (Mg), sulfur (S), calcium (Ca). These inorganics are required in
relatively high amounts (> 0.1% of dry mass) and essential for plant life cycle and
biomass production. In addition, plants need a small amount of micronutrients
(essential elements required in relatively small amounts, 100 mg/kg of dry mass)

5
Recent Perspectives in Pyrolysis Research

such as chlorine (Cl), iron (Fe), boron (B), manganese (Mn), zinc (Zn), copper
(Cu), molybdenum (Mo), nickel (Ni). Trace elements like sodium (Na), silicon
(Si), selenium (Se), titanium (Ti), vanadium (V), cobalt (Co), aluminum (Al) and
other heavy metals may also be present in plant biomass at different levels depend-
ing upon the plant species and the environment [24, 30–32].
Plant biomass has a carbon-to-oxygen (C/O) ratio of almost one. Because of this
high oxygen level, the energy density of biomass is relatively low relative to fossil
fuels. The major component of plant biomass is cellular lignocellulosic material,
which is the non-starch fibrous part of the plant materials. Cellulose, hemicellulose
and lignin are the three major constituents of LCB constituting the cell wall of
plants [5, 15, 21]. The main component of the plant cell wall is cellulose (a linear
homogeneous structural polysaccharide composed of D-glucose units with molecu-
lar weight (MW) > 100,000), which provides structural support. The second most
abundant polymer in LCB is hemicellulose, a ramified heterogeneous structural
polysaccharide composed of D-xylose, L-arabinose, D-mannose, D-galactose and
D-glucose units. The third most abundant polymer in LCB is lignin, a phenylpro-
panoid polymer composed of guaiacyl, p-hydroxyphenyl and syringyl units
[33, 34]. The compositions (cellulose, hemicellulose and lignin) of common
LCB are listed in Table 1. Cellulose macromolecules form tough microfibers that
function as the skeleton material of the cell wall. The inner space is packed with
branched amorphous hemicellulose and lignin linking material. Cellulose connects
with hemicellulose or lignin mainly through hydrogen bonds, while hemicellulose
connects with lignin via both hydrogen and covalent bonds. Lignins and carbo-
hydrates link tightly together in lignin-carbohydrate complexes, which results
in residual carbohydrate or lignin fragments in extracted lignin or hemicellulose
samples. Wooden biomasses are usually rich in cellulose, leaves and grasses are rich
in hemicellulose and the shells are mostly rich in lignin. Cellulose is thermally more
stable than hemicellulose. Knowledge of cellulose, hemicellulose and lignin compo-
sition in LCB can be helpful in controlling the product chemistry [32, 37].
In addition to the three major components, some other compounds present in
LCB include inorganic compounds and organic extractives. These exist as non-struc-
tural components that do not constitute the cell walls or cell layers. Organic extrac-
tives can be extracted by nonpolar solvents (such as toluene and hexane) or polar
solvents (such as water and alcohol). These include fats, waxes, proteins, terpenes,

Lignocellulosic material Cellulose % Hemicellulose % Lignin %

Hardwood stems 40–55 24–40 18–25

Softwood stems 45–50 25–35 25–35

Almond shells 29.0–31.1 28.0–38.0 27.7–35

Corncobs 45 35 15
Grasses 25–40 35–50 10–30

Wheat straw 30 50 15

Flax straw 36.70 34.40 28.90

Leaves 15–32 80–85 0

Sugar cane bagasse 32–44 27–32 19–24

Coastal Bermuda grass 25 35.7 6.4

Switch grass 45 31.4 12

Table 1.
Composition of common LCB [35, 36].

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simple sugars, gums, resins, starches, alkaloids, phenolics, pectins, glycosides, muci-
lages, saponins and essential oils. Often these compounds are responsible for the
smell, color, flavor and natural resistance to rotting of some species. A common clas-
sification divides them into aliphatic compounds (mainly fats and waxes), terpenes
and terpenoids, and phenolic compounds. The inorganic compounds constitute less
than 10% by weight of LCB, forms ash in the pyrolysis process [21, 32].
LCB contains varying amounts of inorganic materials (including alkali and
heavy metals, chlorine, phosphorus and sulfur) collectively called ash. The ash
contents in LCB depend on feedstock type, the environment in which it was
grown, fertilizer use, and contamination with soil particles. Typically, softwood
and hardwood have ash contents below 1 wt%, short-rotation woody crops have
around 2 wt%. Herbaceous crops have high levels of potassium and silicon and
ash contents up to 7 wt%. Ash content is also not uniformly distributed within
biomass; bark has higher concentrations of inorganics [38]. Water in wet bio-
mass contains in three phases: bound water (hygroscopic or adsorbed, in cell
walls, believed to be hydrogen-bonded to the OH groups of primarily cellulose
and hemicelluloses of the biomass); free or unbound water (liquid water in cell
cavities or voids of the biomass if the moisture content is higher than the fiber
saturation point); and water vapor which fills the cell cavities or voids of the
biomass [23]. Depending on the type of LCB, the cellulose, hemicellulose and
lignin content fall in the range 40–60%, 15–30% and 10–25%, respectively. Both
cellulose and hemicellulose are carbohydrates (polymers of sugars) and can be
hydrolyzed into fermentable sugars, which in turn can be converted into fuels
and chemicals. Wood biomass contains much higher amounts of the three main
components (~90%), while agricultural and herbaceous biomass contains more
extractives and ash [21, 32].

2.2.1 Cellulose

Cellulose is the most abundant organic polymer on the planet. It is one of the
main structural constituents of the lignocellulose cell wall of green plants and is
found in an organized fibrous structure. Cellulose is a polysaccharide consisting
of d-glucose (pyranose) units linked by β-1,4 glycosidic bonds. The 𝛽-linkages
in cellulose form linear chains. The degree of polymerization (DP) is about
300–15,000, depending on the plant variety. Cellobiose is the repeating glucose
disaccharide of cellulose. Because of its long and linear molecules, cellulose does
not dissolve readily in water. The chemical formula of cellulose can be written
as (C6H10O5)n, where n is the DP. It is the long flexible natural polymer in fibers
that predominately gives trees and wood of their strength. Cellulose chains
are grouped to form cellulose fibers, which are interlinked by hydrogen bonds
and van der Waals forces, resulting in long microfibrils. These microfibrils are
arranged as a mesh in the cell wall, giving it strength and shape. Hemicelluloses
and lignin cover the cellulose microfibrils. Cellulose is highly stable and resistant
to chemical attack because of the high degree of hydrogen bonding between cel-
lulose chains [15, 32, 37, 39, 40].
The hydroxyl (OH) groups present on the inner and outer surfaces of cellulose
forms intra- and intermolecular hydrogen bonds, which stiffens the chains and
promotes aggregation into a crystalline structure. The crystallinity and stabiliza-
tion of cellulose mainly originate from the presence of OH groups. As three OH
groups are available in each glucose molecule, the inner and outer surfaces of cellu-
lose are covered by OH groups. These OH groups make hydrogen bonds with other
OH groups and other groups (such as O, N and S) available in lignocelluloses. The
crystalline structure of cellulose leads to chemical stability and provides strength

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Recent Perspectives in Pyrolysis Research

and toughness to the roots and stems of a plant. Cellulose molecules have different
orientations throughout the structure resulting in different levels of crystallinity.
The energy of hydrogen bonds in water and cellulose is 15 and 28 kJ/mol, respec-
tively and the energy of van der Waals in water is only 0.15 kJ/mol. The strength
of cellulose mainly originates from the existence of hydrogen bonds rather than
van der Waals forces. The interchain hydrogen bonds introduce order (crystalline)
or disorder (amorphous) into cellulose structure, creating two forms of cellulose:
crystalline and amorphous. Cellulose requires severe hydrolysis conditions for
breaking it into simple glucose units due to its crystalline structure. As suggested
by some authors, cellulose consists of three regions: true crystal, subcrystalline
(disordered structure in true crystal regions) and or noncrystalline (subscrystal-
line) regions. The crystallinity index (CrI) usually characterizes the crystallinity of
cellulose, increasing CrI leads to decreasing chemical and biological hydrolysis of
cellulose [41, 42].

2.2.2 Hemicellulose

Hemicellulose is the second most abundant natural organic polymer after

cellulose on the planet. In contrast to the linear or one-dimensional structure
of cellulose, hemicellulose is a two-dimensional polymer composed of short
chain branched heteropolysaccharides side connections. It is one of the major
constituents of plant cell walls and is strongly linked to the surface of cellulose
microfibrils. Hemicellulose is a random heterogeneous polysaccharide of pen-
toses (xylose and arabinose), hexoses (galactose, glucose and galactose) and
their acidified derivatives such as glucuronic and galacturonic acids. Because
of the branched nature, hemicellulose is amorphous, which is relatively easy to
hydrolyze (by dilute acids, bases and hemicellulose enzymes) to its constituent
sugars compared to cellulose. The content and structure of hemicellulose dif-
fer among LCB. The general nature of the hemicellulose structure depends on
the type of plant, with the result that certain types of lignocellulosic materials
are easier to hydrolyze than others. The various sugar units are arranged with
different substituents and in different proportions. Hemicellulose has a degree of
polymerization of 80–200. It is much smaller than cellulose, with a relatively low
MW (< 30,000). The general chemical formula of hemicellulose can be written
as (C6H8O4)m, where m is the DP. Lateral chains of hemicellulose form the tightly
bound network through hydrogen bonds with cellulose microfibrils. It makes
a highly rigid matrix of the cellulose-hemicellulose-lignin with interaction of
lignin via covalent bonds [15, 32, 37, 39, 43, 44].
The different groups of polysaccharide molecules such as xylans, mannans,
galactans and arabinogalactans make up hemicellulose. Xylan is the most common
polysaccharide in hemicellulose consists of backbone chains that contain a varying
number of D-xylopyranose linked by β −1,4 linkage (70–130 in softwood xylan and
150–200 in hardwood xylan). Mannans are made up of β−1, 4-linked D-mannose
backbone mixed with D-glucose and D-galactose residues. These compounds include
mannan (made up of mannose monomer), galactomannan (made up of mannose
and galactose monomers), glucomannan (made up of mannose and glucose mono-
mers), glucuronic acid (made up of mannose and glucuronic monomers). Galactan
is composed of repeating galactose units as a polymer. Arabinogalactans consist of
arabinose and galactose monosaccharides. The dominant hemicellulose component
in hardwood, agricultural residues and herbaceous crops is xylan, with a small
degree of acetylation and arabinose side groups. The main form of hemicellulose in
softwood is glucomannan, highly acetylated and containing glucose and mannose
[15, 32, 37, 44].

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2.2.3 Lignin

After cellulose and hemicellulose, lignin is the third largest heteropolymer

that occurs predominantly in the cell walls of woody plants. It is the main non-
polysaccharide constituent of plant biomass and the amount of lignin vary widely
with plant species. Lignin primarily consists of macromolecules that contain highly
branched phenolic compounds. Lignin is composed of three different phenyl
propane (three-carbon chain attached to rings of six carbon atoms) monomers,
including coniferyl alcohol (guaiacyl propanol), p-coumaryl alcohol (p-hydroxy-
phenyl propanol) and syringyl alcohol (sinapyl alcohol). The phenyl propane
monomeric units in lignin are linked in different ways (alkyl-aryl, alkyl-alkyl and
aryl-aryl ether bonds): through oxygen bridges between two propyl and phenyl
groups, between a phenyl and a propyl group or through carbon–carbon bonds
between the same groups. Lignin is generally considered as the natural phenolic
glue that tightly binds cellulose and hemicellulose of LCB together; thus, leading
to a strong cell wall structure and making it insoluble in water. The functions of
lignin, an amorphous and highly complex aromatic hydrophobic biopolymer,
are (a) to provide mechanical strength to the plants. It plays a cementing role for
linkages (van der Waals, hydrogen bond and covalent bond) between cellulose and
hemicellulose to form a 3-dimensional structure of lignin-polysaccharide complex
in cell wall leading to a strong cell wall structure; (b) to provide sealing for water-
conducting system linking roots with leaves. Polysaccharide components of the
plant cell wall are hydrophilic and permeable, while lignin is hydrophobic and
impermeable. The cross-linking between polysaccharides and lignin is a barrier for
water absorption to the cell wall that create vascular tissues for efficient conduc-
tion of water in plants. Lignin exists in all vascular plants; and (c) to protect plants
against biodegradation. It forms a natural protective shield protecting cellulose
and hemicellulose in plants and makes plants resistant to pathogens, oxidative
stresses and biodegradation by enzymes and microorganisms [42, 45–47].
The distinctive feature that differentiates lignin from cellulose and hemicel-
luloses is the presence of aromatic monomers. Lignin is less polar than cellulose
or hemicellulose. Physically, cellulose microfibrils encrust hemicellulose whose
empty spaces are filled up with lignin. Lignin is embedded within hemicellulose to
provide additional rigidity to the plant. These lignin-hemicellulose fibers char-
acterize woody plants, whereas the fibers in herbaceous plants are more loosely
bound, indicating a lower amount of lignin [15, 35, 47]. The lignin content of
plants varies with species and age. It is originated from not only content but also
monomeric units and linkage types. The lignin content of softwood is in the range
of 25–40%, which is higher than that of hardwood (18–25%), herbaceous crops
(10–20%) and annual plants (10–12%). LCB with lignin percentage up to 40% has
been reported. Softwood lignin is primarily made from coniferyl alcohol (>95%),
with the rest consisting of coumaryl alcohol derived units and trace amounts of
syringyl alcohol derived units. Hardwood lignin is composed of coniferyl alcohol
and syringyl alcohol derived units in varying ratios. Lignin in grassy biomass has
all three types of monomers. Annual plants lignin is composed of coumaryl alco-
hol. The elemental composition of lignin is approximately 61–65% carbon, 5–6%
hydrogen and the remaining is oxygen. The carbon to oxygen (C/O) atom ratio for
lignin is higher than 2:1, which is at least double that of hemicellulose and cel-
lulose, where the C/O ratio is nearly 1:1. Therefore, lignin is a more energy-dense
substance than polysaccharides. Lignin structure has many polar and hydroxyl
groups allowing the establishment of strong intramolecular and intermolecular
hydrogen bonds. These make lignin insoluble in any solvents except alkaline
solutions [23, 37, 42, 44, 48].

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3. Analysis of biomass

Analysis of biomass feedstock is an integral part of understanding the behavior

of biomass in energy use. The proximate analysis, ultimate analysis and higher heat-
ing value (HHV) of biomass can provide a clear understanding of its thermochemi-
cal conversion characteristics.

3.1 Proximate analysis

The proximate analysis provides information on the biomass in terms of

volatile matter (VM), ash content, fixed carbon (FC) and moisture (M). VM of
biomass is the condensable and non-condensable gases released from the biomass
during heating. The amount of VM depends on the heating rate and the final
temperature to which biomass is heated. Ash is the solid residue left after the
biomass is completely burned. FC shows the percentage of biomass burned in the
solid states, while VM indicates the percentage of biomass burned in the gaseous
state. The ash content indicates the quantity of non-combustible ash remaining
on the fire grates or ash pit or entrained with flue gases. These are of fundamen-
tal importance for biomass energy use and such information for specific LCB
are depicted in Table 2. Such data provides the furnace designer with essential
information for the furnace design, including sizing and location of primary and
secondary air supplies, refractory, ash removal and exhaust handling equipment
etc. [49, 50].
The composition of ash depends on the type of biomass which includes mostly
inorganic residues such as silica, aluminum, iron, calcium and small amounts of
magnesium, titanium, sodium and potassium may also be present. Even though ash
content of biomass is usually very small, it may play a significant role in biomass
combustion or gasification if biomass contains alkali metals (such as potassium) or
halides (such as chlorine). Straw, other agricultural residues and grasses generally
contain potassium compounds and chlorides are particularly susceptible to this
problem and can cause severe agglomeration, fouling and corrosion in boilers or
gasifiers. The ash obtained during biomass conversion does not necessarily come
from biomass itself but also from other sources such as contamination as well.
Biomass can pick up a considerable amount of dirt, soil, rock and other impurities
during collection and handling. These also partly contribute to ash content. FC is

Lignocellulosic Material VM FC Ash Moisture

Hardwood 72.3 25 2.7 7.8

Softwood 70 28.1 1.7 8.8

Almond shells 79.7 4.9 2.3 8.7

Corncobs 80.6 18.2 1.2 9.7

Reed canary grass 82.5 12.1 5.5 4.7

Wheat straw 63 23.5 5.5–13.5 8.5

Flax straw 80.3 8.8 3.0 7.9

Hazelnut seedcoat 71.20 27.0 1.8 6.8

Sugar cane bagasse 84.00 1.64 4.5–9 8.5

Elephant grass 65 14.66 6.0 10

Table 2.
Proximate analysis (wt%) of common LCB [35].

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the solid carbon (non-volatile) in the biomass that remains in the char in the
pyrolysis process after devolatilization. The amount of FC is related to VM, mois-
ture (M) and ash by the equation: FC =1 − M − VM − ASH [18, 49].
The relationship between FC and charcoal yield in biomass is positive, while VM
and ash relate negatively to charcoal yield. It is expected that the greater biomass VM
lead to greater gas production instead of the solid phase. Moisture content will have
a significant impact on the biomass conversion process. High moisture content is a
major concern in biomass. Biochemical conversion processes can use biomass with
high moisture content, while thermochemical conversion processes generally require
biomass with low moisture content. However, gasification processes require some
moisture to produce hydrogen and the amount of hydrogen produced will increase
with moisture content. The moisture content of some biomass, such as water hya-
cinth, can be very high (> 90%). As the energy used in evaporation is not recovered,
moisture drains much of the deliverable energy during conversion [49–51].

3.2 Ultimate analysis

The ultimate analysis provides the composition of biomass, including major

elements (C, H, O, S, N and Cl), moisture and ash on a gravimetric basis. The
ultimate analysis of common LCB are listed in Table 3. The ultimate analysis is
generally reported on a dry and ash-free basis. These are useful in understanding
biomass processes and performing mass balances on biomass conversion processes.
Elemental chemical composition, moisture, ash and volatiles are essential for
thermal/ thermochemical conversions of biomass. Additional information on the
polymeric composition of biomass is important for conversions like torrefaction,
pyrolysis and gasification. A typical ultimate analysis of the biomass in terms of its
basic elements, moisture (M) and inorganic constituents (ASH) can be written as:
C + H + O + N + S + ASH + M = 100% . The hydrogen or oxygen content in the
ultimate analysis includes only the hydrogen and oxygen present in the organic
components of the biomass it does not include the hydrogen and oxygen in the
moisture. The moisture in the biomass is expressed separately as M. The ultimate
analysis is useful in calculating the quantity of combustion air required to sustain the
combustion reactions. Generally, sulfur and nitrogen content of biomass is very low.
As a result, biomass produces minimal SOX and NOX pollutants. Particulate emis-
sions of unburned carbon in the flue gases can present pollution problems [49, 51].

Lignocellulosic Material C H N S O
Hardwood stems 48.6 6.2 0.4 — 41.1

Softwood stems 52.1 6.1 0.2 — 41.0

Almond shells 54.7 7.5 0.3 0.3 37.4

Corncobs 43.6 5.8 0.7 1.3 48.6

Grasses 48.3 5.7 0.8 — 39.4

Wheat straw 53.9 7.0 3.0 — 36.1

Flax straw 43.10 6.20 0.68 0.09 49.90

Hazelnut seedcoat 52.90 5.6 1.4 42.7

Sugar cane bagasse 45.13 6.05 0.3 — 42.77

Switch grass 48.6 5.5 0.5 39.5

Table 3.
Ultimate analysis (wt%) of common LCB [35].

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4. Biomass conversion

Biomass conversion is the key step to produce heat, biofuels or chemicals from
LCB. Biomass can be converted to these products through chemical, biochemical
and thermochemical conversion processes. Selection of the conversion process
depends on number of factors, including the desired form of end products (heat,
biofuels or chemicals), biomass feedstock (type, quantity and characteristics) avail-
able, environmental standards, policy, economic conditions and specific factors
related to the project. In most situations, the selection is based on two main fac-
tors, i.e., desired form of end products and the available feedstocks [5, 21, 52]. The
moisture content of biomass primarily determines the conversion process for the
selected biomass. Thermochemical conversions like pyrolysis, gasification or com-
bustion are ideal for dry biomasses such as wood or straw. These processes are often
unsuitable for wet biomass because of low energy density due to high moisture con-
tent. The high moisture content significantly increases the transportation cost and
energy cost for drying. Wet conversion processes such as hydrothermal processing
and biochemical processing (fermentation and anaerobic digestion) have gained
growing attention and are more suitable to process high moisture content biomass
like aquatic biomasses, sewage sludge, food waste and manures. Despite consuming
less energy, biochemical conversion processes require more time compared to ther-
mochemical conversion processes. Subsequently, much attention has been placed on
hydrothermal processing, which is more cost-effective than conventional thermal
drying followed by thermochemical conversion. The additional parameters (like
cost and feasibility of drying etc.) need to be considered when selecting the correct
conversion process, primarily if the moisture content lies between wet and dry
regions [6, 21, 53, 54]. Biomass has substantial quantities of free and bound water.
Wet biomass requires drying before pyrolysis, gasification or combustion; hence,
additional energy and facilities are needed. Drying biomass outside the pyrolysis
reactor is beneficial (produce pyrolysis vapor with high calorific value and bio-oil
with low water content) [23].
The important biochemical conversion processes include anaerobic/aerobic
digestion, fermentation and enzymatic or acid hydrolysis. In biochemical conver-
sion, biomass molecules are broken down into smaller molecules by bacteria or
enzymes. This process is much slower than the thermochemical conversion process
but does not require much external energy. In anaerobic digestion, bacteria take
oxygen from the biomass itself instead of atmospheric oxygen. The products of
anaerobic digestion are biogas (a mixture of methane, carbon dioxide) and solid
digestate. Only 5–10% of the feed into the digester is digested by the anaerobic
bacteria. The digestate consists of remaining indigestible material. Aerobic diges-
tion, commonly known as composting, takes place in the presence of oxygen. It
uses different types of microorganisms that access oxygen from the air, producing
carbon dioxide, heat and solid residue (compost). In fermentation, starch is con-
verted into sugars using acids or enzymes. Then sugar is converted into ethanol or
other chemicals with the help of yeast. The fermentation of lignocellulosic feed-
stock requires additional pretreatment (hydrolysis) to breakdown the cellulose and
hemicellulose into simple sugars. Hydrolysis can be achieved by the use of acids,
enzymes or hydrothermally [5, 21, 52].
The lignin is not converted and is left for thermochemical conversion. Major
thermochemical conversion processes include combustion, gasification, pyrolysis,
torrefaction and hydrothermal processing. These are further discussed in the
following sections. Thermochemical conversions generally offer many advantages
over biochemical conversions, such as handling a wide variety of feedstocks, better

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conversion efficiency, high energy efficiency and shorter reaction times. As a result,
in recent years, thermochemical conversions have received greater attention for
biofuels production [3, 21].

5. Thermochemical conversion

There are many types of thermochemical conversion processes through which

biomass is converted to solid, liquid and gaseous products. Thermochemical
conversion processes use high temperatures to breakdown the bonds of organic
matter. Thermochemical conversion routes can be classified according to the
oxygen content used in the process, including combustion (complete oxidation),
gasification (partial oxidation) and pyrolysis (thermal degradation in the absence
of oxygen). Torrefaction is also performed in the absence of oxygen. Hydrothermal
processing is an alternative route to process wet biomass using heat and pressure
in the presence of water, which can also be considered a thermal degradation in
the absence of oxygen. The typical products of thermochemical conversion of
biomass are carbon-rich solid residue (biochar), condensable vapors (bio-oil or
tar) and non-condensable gases. The distribution of products (biochar, bio-oil/tar
and gases) depends primarily on the conversion process [21]. A brief description of
biochar, bio-oil and gases are given below.
Biochar - Biochar is a porous carbonaceous material with a high degree of
aromatization and strong antidecomposition ability. The physical, chemical and
mechanical properties of biochar will depend on the feedstock material characteris-
tics and pyrolysis conditions used for the production of biochar. It has a wide range
of potential applications in various agronomic and industrial sectors. Biochar is
used in agriculture to upgrade the soil quality, in waste treatment to remove organic
contaminants, heavy metals and different types of dyes and pigments from textile
industries and in power generation as a fuel. The most successful approach for high-
yield biochar production is via slow pyrolysis [21].
Bio-oil - Bio-oil is a dark brown, free-flowing organic liquid mixture. It generally
comprises of 15–35 wt% water (resulting from both the original moisture and as
a pyrolysis product) and a mixture of organic compounds, such as acids, alcohols,
ketones, aldehydes, phenols, ethers, esters, sugars, furans, alkenes, nitrogen
compounds, miscellaneous oxygenates and solid particles. The final water content
of bio-oils depends on the initial moisture content of biomass feedstock and water
formation during pyrolysis. Water cannot be removed from bio-oil by conventional
methods like distillation. Bio-oil has a low (15–20 MJ/kg) HHV in comparison to
conventional petroleum fuel HHV of 42–45 MJ/kg due to the increased oxygen
content (35–40 wt% on a dry basis). Bio-oil density is approximately 1200 kg/m3;
the viscosity ranges from 25 to 1000 cP (depending on the composition). It is acidic
in nature (pH value of 2–4) due to the presence of organic acids such as formic and
acetic acid and, hence, corrosive. Bio-oil has a large amount of oxygenated com-
pounds and organic material; it is highly polar. As a result, bio-oil is hydrophilic.
A distinct aqueous phase is only observed with bio-oil having water content in the
range 30–45 wt% [23, 55]. Bio-oil will not mix with hydrocarbon liquids. Bio-oil
has a complex mixture of oxygenated compounds that provide the potential and
challenge for its utilization. It has a range of uses in energy applications, can be
used in boilers for heat and power generation, cofired with natural gas/coal in
power plants or blended with other fuels such as ethanol or gasoline. Bio-oil can be
converted into fuels (ethanol and diesel) and chemicals through hydrocracking/
hydroprocessing [56].

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Non-condensable gases – Gases produced in biomass pyrolysis may consist of car-

bon dioxide (CO2), carbon monoxide (CO), hydrogen (H2), methane (CH4), ethane
(C2H6) and ethylene (C2H4), and small amounts of other gases, such as propane
(C3H8), ammonia (NH3), nitrogen oxides (NOX), sulfur oxides (SOX) and alcohols
of low carbon numbers. The composition of the non-condensable gases will be
determined by the pyrolysis temperature and the vapors condensing temperature.
Lower pyrolysis temperatures (such as torrefaction) result in higher amounts of
CO and CO2, while higher pyrolysis temperatures result in increased content of
CH4 and H2.

5.1 Combustion

Combustion is simply the burning of biomass in air. Chemically it is high-

temperature exothermic oxidation of biomass in the presence of oxygen. Complete
combustion of biomass involves the production of heat due to the oxidation of
carbon and hydrogen of biomass to CO2 and H2O, respectively. The process consists
of consecutive heterogeneous and homogeneous reactions. Biomass combustion
basically depends on the properties of the feedstock and particle size, temperature
and combustion atmosphere. Char (contains some organic carbon) and ash (typi-
cally includes inorganic oxides and carbonates) are the solid byproducts of combus-
tion. Combustion temperatures are usually in the range of 700–1400°C [52, 57].
Energy stored in biomass can be converted into heat and power via combus-
tion. The chemical composition and the combustion properties of biomass vary
considerably depending on the biomass type. A wide range of biomass sources can
be considered for combustion. Seasonal, regional variances and parts of the plant
(bark, branches and leaves etc.) of the woody biomass (wood chips, wood pellets
and waste woods etc.) can result in differences in the chemical composition of the
feedstock. Straw is also considered as having potential as an alternative feedstock.
Straw is essentially a waste product from agricultural crop production. This feed-
stock does not compete with agricultural products for the limited land resources.
Besides wood and straw, a wide variety of waste products such as rice husks, wheat
bran, peanut shells, coffee grounds, bagasse, etc., can be used as feedstock. These
can be used as an inexpensive fuel to produce heat or electricity needed for indus-
trial processes. The best quality fuels contain high amounts of carbon and hydrogen
and low amounts of other elements (oxygen, nitrogen, sulfur and trace elements).
Biomass usually contains higher levels of oxygen than fossil fuels. Impurities such as
sulfur and nitrogen are associated with the emission of SOX and NOX. Trace ele-
ments such as potassium and sodium can cause fouling; chlorine leads to corrosion
and silica causes excessive wear to milling equipment [52, 57].
Fresh woodchips can contain 50% moisture and leaves can be over 90% mois-
ture. Most furnaces and boilers recommended biomass with less than 20% mois-
ture. It is extremely difficult to maintain combustion with a moisture content of
more than 55%. Higher levels of moisture affect combustion efficiency and increase
the amount of smoke emitted. The water content also increases the combustion
time of a biomass particle and, thus, extends the required residence time in a boiler/
furnace. Torrefaction upgrades biomass by removing lighter volatiles and moisture.
It improves the heating value of biomass, increases the hydrophobicity and stability
and, thus, can be stored under the open sky [52, 57].
Combustion can be split into four stages: drying, pyrolysis (devolatilization),
volatiles combustion and char combustion. When biomass particles enter a hot
environment, moisture in the particles starts to evaporate. On further heating,
volatile gases and tars are released from biomass particles, followed by the combus-
tion of volatiles. The remaining char will essentially retain its original shape. In the

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char combustion stage, char reacts with oxygen to form mainly CO2 (and CO due to
incomplete combustion) and ash remains after combustion is completed. Detailed
chemical reactions kinetics that takes place during biomass combustion are complex
[52, 57, 58].
The initial combustion stage requires heat to evaporate moisture; hence, it is
necessary to have biomass with minimal moisture content. Biomass has a signifi-
cantly higher volatile matter content compared to coal and the fixed carbon to
volatile matter (FC/VM) ratio is significantly low. Lower values of the FC/VM
ratio leads to high ignition behavior. Biomass releases VM at a lower temperature
and more rapidly than coal, thus, reducing ignition temperature compared to coal.
Proper design of the air supply is important due to the faster release of VM in order
not to delay combustion. Combustion of VM is fast compared to combustion of
solid charcoal and a low ratio of FC/VM decreases the residence time in the boiler/
furnace [52, 57, 58].
Incomplete combustion results in the formation of intermediates, including
pollutants such as CO, CH4 and particulate matter (PM). Ash handling, high emis-
sions of NOX, SOX, CO2 and particulate matter make combustion environmentally
challenging. Biomass is more corrosive, tends to foul heating surfaces, ash from
biomass tends to agglomerate. The boilers have to be redesigned to burn biomass
properly. Depending on the condition and combustion properties of the biomass to
be burned, different furnace designs and combustion parameters can be selected to
ensure optimum efficiency. Direct combustion is currently the principal method of
generating electricity around the world [52, 57, 58].

5.2 Gasification

Biomass gasification is a thermochemical process of converting solid biomass

into a gaseous fuel known as synthesis gas or producer gas under a reduced oxygen
atmosphere to avoid complete combustion [59, 60]. Gasification aims to maximize
the conversion of biomass feed into useable gases. In the gasifier, feed is exposed to
a high temperature atmosphere, which heats the biomass leading to thermal decom-
position. In contrast to pyrolysis, the feed is brought into contact with a gasifying
agent (air). At the gasifier temperature, reactions between oxygen and carbon
take place. A mixture of many gases, primarily carbon monoxide and hydrogen, is
released as the output product of the gasification process. The gas contains vari-
ous percentages of CO, H2, CH4, CO2, H2O and N2 depending on the quality of the
biomass used and the way gasification is conducted. It also produces liquids (oils,
tars, and other condensates) and solids (char, ash) from solid biomass feedstocks
[5, 61, 62]. A simple way of representing the gasification reaction is shown below

Biomass + O2 ( g ) → CO ( g ) + H2 ( g ) + CO2 ( g ) + CH4 ( g )

+ Tar ( l ) + H2O ( l ) + Char ( s ) + TraceSpecies (1)

Gasification processes are designed to generate fuel or synthesis gases as the

primary product that can be used in internal and external combustion engines as
well as fuel cells, offering a viable solution to overcome energy demands. Currently,
such syngas is used as fuel to generate heat and electricity or as a feedstock for many
products in the petrochemical and refinery industries, like methanol, ammonia,
synthetic gasoline, etc. The overall gasification process is endothermic, requiring
energy input for the reactions to proceed, most of which operate between 600°C
and 1500°C [59, 63]. The energy needed for this endothermic reaction is obtained
by oxidation of part of the biomass through a direct heating (autothermal) or an

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indirect heating (allothermal) phase. The main operating parameters of gasification

include type and design of gasifier, gasification temperature, flow rates of biomass
and oxidizing agents (air or steam), type and amount of catalysts, and biomass type
and properties [64]. In addition to the operating conditions of the gasifiers, the
properties of biomass such as size, shape, density, chemical composition, energy
content and moisture content affect biomass gasification. Gasifier reactors are
simple in construction and their designs are generally categorized into the following
types: downdraft, updraft, entrained flow, and fluidized bed.
If air is used as the gasifying agent, the producer gas is usually diluted by
atmospheric nitrogen. As a result, producer gas has a relatively low calorific value
of 4–6 MJ/m3 (normal cubic meter) compared to the calorific value of natural gas
of 39 MJ/m3. Because of its low calorific value, larger volumes of producer gas are
required to achieve a given energy output compared to natural gas. In some more
applications, oxygen-enriched air, oxygen or even steam may be used as the gasify-
ing agent, resulting in the production of syngas with higher calorific value in the
range of 10–15 MJ/m3 due to the absence of diluting nitrogen [16].

5.3 Pyrolysis

Pyrolysis is a thermal decomposition process that takes place in the absence

of oxygen to convert biomass into three distinct product fractions: solid residue
(biochar), condensable vapors resulting liquid product fraction (bio-oil) and non-
condensable gaseous products. Once oxygen is removed, combustion cannot occur;
instead, pyrolysis happens. Pyrolysis temperatures are usually between 300 and
700°C, depending on the pyrolysis process employed. Pyrolysis is the most promis-
ing technique to convert biomass into biochar and bio-oil. Lower pyrolysis tempera-
tures and longer residence times tend to produce more biochar. High temperatures
and longer residence times increase the production of gas. Moderate temperatures
and short residence times tend to produce more liquids. Higher pyrolysis tempera-
tures tend to produce a higher proportion of aromatic carbon [65, 66].
Depending on the operating conditions (heating rate, solid residence time and
temperature), pyrolysis processes are classified as torrefaction, slow (conventional)
pyrolysis, intermediate pyrolysis, fast pyrolysis, flash pyrolysis, and microwave
pyrolysis. Various operating conditions are used in these processes; residence time
can vary from less than 1 second to hours, heating rate can vary from less than 1°C/s
to more than 1000°C/s and temperature ranges from 300 to 700°C or higher. As
each type of pyrolysis produces different proportions of the three types of products
(biochar, bio-oil and gas), careful selection of the pyrolysis process is essential to
obtain the final desired product [21].
The primary conversion of biomass during the pyrolysis process can be
described by three pathways; char formation, depolymerization and fragmenta-
tion. Char formation is generally favored by intra- and intermolecular rearrange-
ment reactions resulting in higher thermal stability of the residue. This pathway is
characterized by the formation of benzene rings and the combination of these rings
into an aromatic polycyclic structure. These rearrangement reactions are generally
accompanied by the release of water or non-condensable gas (devolatilization).
Depolymerization is a dominant reaction during the initial stages of pyrolysis,
characterized by the breaking of polymer bonds. This occurs when the tempera-
ture is sufficiently greater than the activation energies for the bond dissociation.
Depolymerization increases the concentration of free radicals. It is followed by
stabilization reactions to produce monomer, dimer and trimer units. These volatile
molecules are condensable at ambient conditions and found in the liquid fraction.
Fragmentation consists of breaking polymer bonds and even monomer bonds result

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in the formation of non-condensable gases and a range of organic vapors that are
condensable at ambient conditions [55, 58, 67].
The decomposition of cellulose, hemicelluloses and lignin releases a mixture of
condensable vapors and non-condensable gases. The condensable vapor contains
(apart from water vapor) methanol, acetic acid, acetone (all three mainly from
hemicellulose), hydroxyacetaldehyde, anhydrous monosaccharides (both mainly
from cellulose), phenols and heavier tars (from lignin decomposition). The heavier,
water-insoluble tars contain larger molecular fragments obtained after splitting the
ether and C-C bonds in lignin. The resulting complex mixture, once condensed,
is referred to as bio-oil. The main parameter that determines the degree of devola-
tilization of the biomass is the pyrolysis temperature. Yang et al. [68] observed
great differences among the pyrolysis behaviors of the three components, cellulose,
hemicellulose and lignin. These three forms of polymers are responsible for most
of the physical and chemical property modification during the pyrolysis process.
The mechanisms of pyrolysis of these polymers are chemically different from
biomass species to species. Cellulose and hemicellulose decompose over a narrower
temperature range, whereas lignin degrades over a wider temperature range than
cellulose and hemicellulose. Pyrolysis of lignin is known to produce more biochar
than pyrolysis of cellulose and hemicellulose. Biomass pyrolysis consists of three
main stages: (a) initial evaporation of moisture, (b) primary decomposition and
(c) secondary reactions (oil cracking and repolymerization). At the initial heating
stage, when the biomass temperature is increased to about 100°C, the mass of bio-
mass decreases due to the evaporation of free water. Bound water is then removed in
heating the biomass to temperatures up to 160°C. At this stage, the heating value of
pyrolysis gases is negligible. Thermal decomposition of biomass begins with devola-
tilization/ decomposition of extractives at temperatures <220°C. Hemicellulose is
the least stable polymer and breaks down first at temperatures of 220 to 315°C with
maximum mass loss at 268°C [23, 38, 55, 67, 68].
The reactions are endothermic between 180 and 270°C, sometimes becoming
exothermic at temperatures above 280°C. The nature of pyrolytic decomposition
reactions explains this phenomenon. Devolatilization and decomposition in pyroly-
sis is not a single step reaction and a difference can be made between primary and
secondary reactions. The gas and vapor products of primary conversion are unsta-
ble under pyrolysis temperatures and, with sufficient residence time, can undergo
secondary reactions such as cracking and/or repolymerization of primary volatile
compounds. Cracking reactions consist of the breaking of volatile compounds into
lower MW molecules. Repolymerization involves combining volatile compounds
into higher MW molecules, which may not be volatile under pyrolysis temperatures.
Repolymerization reactions become effective at later stages of pyrolysis, leading to
the formation of char. It also results in the formation of secondary char. Primary
char can act as a catalyst to the secondary reactions. Primary reactions are highly
endothermic, while secondary reactions are exothermic and result in the produc-
tion of secondary char and non-condensable gases at the expense of volatiles in
the vapor phase. Decomposition of vapors to coke and secondary vapors has been
suggested as the reason for exothermicity. The extent of secondary decomposition
reactions determines the overall exothermicity of the pyrolysis reaction and the
overall char (primary and secondary) yield. The occurrence of primary and second-
ary reactions in the thermal decomposition of biomass highlights the fundamental
difference between fast pyrolysis and slow pyrolysis [38, 55, 67].
Cellulose has a high degree of polymerization and exhibits higher thermal
stability. It decomposes in the temperature range 315 to 400°C. The secondary
reactions continue to occur within the solid matrix with further increasing of
the temperature. At temperatures above 400°C, the less volatile components are

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gradually driven off from solid char residue resulting in higher fixed carbon content
and lower volatile carbon content of the solid char residue. As the temperature
increases above 600°C, the condensable vapor components undergo cracking and
polymerization reactions, resulting in a lower bio-oil yield. Lignin is the most dif-
ficult component to pyrolyse, which decompose in a wide temperature range from
160 to 900°C, the rate of lignin degradation reactions is slower than cellulose and
hemicellulose [23, 38, 55, 68].
The combination of low heating rate and longer residence time allowed for repo-
lymerization reactions to maximize biochar yield. A low temperature, high heating
rate and short gas residence time would be required to maximize bio-oil yield. A
high temperature, low heating rate and long gas residence time would be preferred
to maximize the gas yield. As a result of high heating rates and short residence
times, fast pyrolysis tends to yield higher proportions of bio-oils. In contrast, slow
pyrolysis produces higher proportions of biochars because of slow heating rates and
longer residence times. Pyrolysis requires relatively dry feedstock (usually moisture
content <30 wt%, but moisture contents of ~10 wt% are preferred) and ground to
different particle sizes based on the type of pyrolysis. Feedstock with high moisture
content consumes more energy to account for increasing heat of vaporization
during the heating of biomass towards the pyrolysis temperature. Additionally, the
gases and vapors produced in pyrolysis using a high moisture feedstock are diluted
with steam and have a lower calorific value [21, 61].
The molar H/C and O/C ratios of LCB are approximately 1.5 and 0.7, respec-
tively. During pyrolysis, the biomass undergoes devolatilization and the solid
portion gets enriched in carbon. The H and O are preferably removed over C and
the H/C and O/C ratios tend to decrease as biomass undergo its transformation into
biochar. The H/C and O/C ratios are used to assess the degree of aromaticity and
maturation. Low-temperature chars have high H/C and O/C ratios, the values close
to the original biomass. After pyrolysis, a significant decrease in the H/C and O/C
atomic ratios is reported and it decreased straightly with increasing pyrolysis tem-
perature. When the pyrolysis temperature is below 500°C, the reduction in H/C and
O/C is mainly attributed to major decomposition reactions of biomass, including
dehydration (water removal), decarboxylation (CO2 removal) and decarbonylation
(CO removal). Above 500°C, the H/C ratio decreases drastically compared to the
O/C ratio, which indicated direct dehydrogenation and demethanation of the chars
occurred [38, 69].

5.3.1 Torrefaction

Torrefaction is a pretreatment for upgrading biomass primarily for energy

production. Torrefaction, a mild or incomplete form of pyrolysis, involves heat-
ing the feedstock to temperatures of 200 to 300°C at slow heating rates (less than
1°C/s) in the absence of air under atmospheric pressure conditions. The residence
time depends on the particle size and ranges between several seconds and an hour.
Torrefaction removes water as well as superfluous volatiles and partly decomposes
the biopolymers (cellulose, hemicelluloses, and lignin) by giving off organic vola-
tiles. It tends to yield higher proportions of solid (torrefied biomass) in addition to
liquid and non-condensable gaseous products [21]. Decomposition can be further
subdivided into (a) drying, (b) depolymerization and recondensation, (c) limited
devolatilization and carbonization, (d) extensive devolatilization and carboniza-
tion. Hemicellulose is the least stable of three major polymers, soften between 150
and 200°C and break down via various dehydration, deacetylization and depoly-
merization reactions at processing temperature range 200–300°C. Predominant
hardwood hemicellulose is xylan, while predominant softwood hemicellulose is

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glucomannan. Xylan tends to break down more quickly than glucomannan at lower
temperatures. Therefore, hardwood has a higher mass loss (higher breakdown of
hemicellulose) than softwood when treated at the same temperature. This indicates
that different biomass species have different torrefaction kinetics. The cellulose
and/or lignin degradation during torrefaction is small. A greater degradation has
been reported at temperatures above 270°C. Different biomasses have different
physical properties such as porosity, specific heat capacity, thermal conductivity,
particle size distribution etc., which results in non-homogenous torrefied biomass.
A narrower particle size distribution is required for efficient torrefaction and
optimized product quality [23, 70].
As specified by the EBC [71], the molar oxygen to carbon (O/C) ratio of bio-
char should be less than 0.4. But torrefied biomass tends to have higher oxygen
to carbon (O/C) ratio than the ECB specification of biochar. Therefore, torrefied
biomass cannot be referred to as biochar. Torrefied biomass has physicochemical
properties in between that of raw biomass and biochar. Torrefaction is a pretreat-
ment method that is used primarily for moisture removal and densification of
biomass, which will reduce the cost of transportation and increase the heating
value of biomass. Torrefaction has higher conversion efficiencies compared to slow
pyrolysis. Torrefied biomass yield has a maximum of 35 wt% (on a weight basis of
dry, ash-free biomass feedstock). A typical mass yield from torrefaction is 70–80%
and energy yield is 80–90%. The lower heating value (LHV) of torrefied biomass
is about 20.4 MJ/kg compared to the LHV of charcoal between 28 and 33 MJ/
kg. Torrefaction increases the hydrophobicity, stability, grindability and reduces
biodegradability compared to the untreated biomass feedstock. Torrefied biomass
can be stored long-term without degradation [21].
The heating value of torrefied biomass on a weight basis increases compared to
its original biomass. Its heating value on a volume basis is not necessarily increased
as torrefied biomass has relatively low bulk density. Torrefied biomass can be
pelletized or briquetted to account for low bulk energy density. Consequently, bulk
energy densities between 14.9 and 18.4 GJ/m3 can be achieved.

5.3.2 Slow pyrolysis

Slow pyrolysis is characterized by moderate temperatures (300–550°C), slow

heating rates (0.1–0.8°C/s) and longer residence time (5–30 min or even 25–35 h)
[56]. Slow pyrolysis aims at maximizing the yield of biochar by promoting sec-
ondary reactions, which is achieved by longer vapor residence times. The biochar
produced in slow pyrolysis consists of both primary and secondary char. The slow
heating rate with moderate pyrolysis temperatures also promotes the production
of biochar. Biochar yield and physicochemical properties depend on the feedstock
properties and pyrolysis conditions such as processing temperature, heating rate
and pyrolysis environment. In addition, moisture content and particle size also
significantly affect biochar yield [28, 56, 72].
The biomass composition plays a significant role in the resulting biochar yield
and the physicochemical nature of the biochar. Biomass cell wall constituents (cel-
lulose, hemicellulose and lignin) behave differently in terms of decomposition and
devolatilization in pyrolysis. As lignin decomposes at lower reaction rates and con-
tains aromatics, it is known to contribute to high biochar yields in slow pyrolysis.
Consequently, if high biochar yield is required, then lignin-rich biomass feedstocks
are preferable. The extractives in biomass will evaporate and end up in the vapor
phase or may be cracked, thereby contributing to char and non-condensable gas
formation [38]. High ash contents in the biomass affect the slow pyrolysis process
and the physicochemical properties of biochar in multiple ways. Alkaline and earth

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alkaline metals exhibit catalytic activity in pyrolysis. They catalyze secondary

reactions of primary vapor components favoring higher yields of non-condensable
gases and biochar or they may catalyze different primary decomposition reactions
altogether. Biomass containing more minerals yields less biochar [67, 72–74]. Most
of the constituents in ash (mainly the alkaline and heavy metals) are non-volatile
within the range of temperatures typically employed in slow pyrolysis processes.
Thus, ash remains in the solid biochar product, potentially affecting the use of
biochar in downstream processes. If biochar (with high ash content) is used in com-
bustion or gasification processes, slagging and equipment fouling occurs. Chlorine
and sulfur lead to higher corrosion. Some downstream applications, such as soil
amendment, can benefit from higher ash contents in biochar (nutrient recycling).
High ash content biochar can be treated with leaching, which involves soaking of
biochar in hot water or hot dilute acid. Washing with pure water at 80°C is suf-
ficient to remove about 90% of the potassium found in biochar, produced at 550°C.
The leaching process has been successfully applied to treat potassium and chlorine
of biochar. Extra dewatering and drying processes are required after leaching in
addition to handling and treatment of leachate, which may contain heavy metals
extracted from biochar [38].
The process variables that affect the biochar yield and properties include pyroly-
sis temperature, heat transfer (to and in the biomass), biomass residence time and
operating pressure. The primary biomass constituents (hemicelluloses, cellulose
and lignin) undergo decomposition and devolatilization over different temperature
ranges. Decomposition of hemicellulose occurs at temperatures below 300°C. The
resulting gas and vapor products include non-condensable gases (such as CO, CO2,
H2 and CH4), water vapor and low MW oxygenated organic compounds (mainly
acetic acid, formic acid, methanol, acetone and furfural). Extensive devolatilization
of lignin and cellulose occurs at temperatures higher than 300°C (slow pyrolysis
temperatures). Peak devolatilization occurs at temperatures around 500°C, yielding
typical vapor products including levoglucosan, hydroxyacetaldehyde, acetic acid
and hydroxymethyl furfural (HMF) all originate from cellulose [38, 74, 75].
Phenolic compounds (both in monomeric and oligomeric form) are typically
liberated from lignin [76]. Further increase in temperatures causes secondary vapor
phase cracking reactions to dominate, yielding additional non-condensable gases
and secondary biochar. The higher the pyrolysis temperature, the lower the biochar
yield. The additional secondary char formation occurring at higher temperatures is
offset by further devolatilization of the primary biochar. The net effect is a decreas-
ing biochar yield with increasing slow pyrolysis temperature. Slow pyrolysis uses
low heating rates resulting in biomass conversion being rate limited by heat transfer.
Additionally, the slow devolatilization resulting from a slow heating rate ensures
maximum secondary char formation. The heat transfer is of less critical importance
in slow pyrolysis (compared to fast pyrolysis) as very long biomass residence times
are used [38]. Biochar yield increases with increasing residence time, decreasing
pyrolysis temperature and lower heating rate. With increasing residence times,
vapors are restrained and reacted with solid-phase extensively for more biochar
yield [28, 56, 72].
Slow pyrolysis favors biochar production at the expense of bio-oil production.
The biochar, bio-oil and gas yields are typically 35 wt%, 30 wt% and 35 wt%,
respectively. The overall slow pyrolysis process can generally be exothermic due
to the extensive occurrence of secondary reactions. Slow pyrolysis can accept a
wide range of particle sizes (5–50 mm). Large biomass particles are frequently
used when rapid heating rates are not required or when the desired product is
biochar [21, 55].

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5.3.3 Intermediate pyrolysis

In intermediate pyrolysis, the reaction is faster than slow pyrolysis but slower
than fast pyrolysis. Intermediate pyrolysis differs from fast pyrolysis in terms of
heat transfer to biomass feed. It occurs in the temperature range of 450–550°C and
even lower temperatures are used (350°C). The heating rates are much lower than
fast pyrolysis (100 to 500°C/min) with residence time ranging from 10 to 30 s and
produce less biochar than slow pyrolysis [65, 77]. Intermediate pyrolysis occurs
at controlled heating rates, thus, inhibiting the formation of high MW tars and
yielding products (biochar, bio-oil and gases) with different product qualities. In
intermediate pyrolysis, the biomass particles sizes and shapes are less critical than
in fast pyrolysis. It can process a wider variety of biomass, larger particles up to
pellets, chips and dust and also material with a water content of up to 40%. High
cooling rates are needed for the vapors to reduce thermal post-decomposition
reactions. A higher amount of bio-oil than slow pyrolysis can be produced through
intermediate pyrolysis. More controlled chemical reactions occur and, thus, the
reaction conditions offer a broad range of variation for process optimization. The
typical product distribution of intermediate pyrolysis is 40–60% of bio-oil, 20–30%
non-condensable gases and 15–25% biochar [77].
The biochars produced by intermediate pyrolysis have a high carbon and low
volatile contents. The bio-oil produced by intermediate pyrolysis has a high calorific
value; the oil fraction easily separates into organic and aqueous phases. Compared
to bio-oil generated from fast pyrolysis, the liquid fraction from intermediate
pyrolysis has some beneficial characteristics, including low tar yield, improved
viscosity and heating value. These characteristics may result from a relatively long
residence time and contact with biochar [78]. Intermediate pyrolysis at 400°C
yielding 35% solid (biochar), 46% liquid and 19% gaseous products has been
reported. The liquid fraction separates into an aqueous phase (38% with 50% water;
HHV of 7 MJ/kg) and organic phase (8% pyrolytic lignin, phenols, etc., HHV of
24 MJ /kg) [79].

5.3.4 Fast pyrolysis

The fast pyrolysis typically involves high heating rates (10–1000°C/s), short
residence times (0.5–2 s) [56] and temperatures between 450 and 550°C. It decom-
poses biomass quickly to generate liquid (bio-oil), solid (biochar) and gaseous
products. The bio-oil, biochar and gas yields are typically 60–70 wt%, 12–15 wt%
and 13–25 wt% on a dry basis, respectively [55].
Fast pyrolysis suppresses secondary reactions from taking place by having short
vapor residence times (rapid removal and quenching of the condensable primary
volatile vapors) and maintaining high biomass heating rates, thereby maximizing
the yield of condensable vapors (bio-oil). In this way, secondary reactions of crack-
ing and repolymerization are prevented. The intermediate products of flash degra-
dation of hemicellulose, cellulose and lignin are rapidly quenched and condensed to
bio-oil before further reactions break down higher MW components into gaseous
products. This freezing of intermediates results in bio-oil containing many reactive
species, contributing to its unusual characteristics. Condensable vapors are formed
by rapidly and simultaneously depolymerizing and fragmenting cellulose, hemicel-
lulose and lignin fractions with a rapid increase in temperature. Rapid quenching
traps many of these products that would further react (depolymerize, decompose,
degrade, crack or condense with other molecules) to form more non-condensable
gases if the residence time at high temperature was extended [61, 80].

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The distribution of products (bio-oil, biochar and gases) depends on the

biomass composition and rate and duration of heating. If bio-oil is the product of
interest, the optimum pyrolysis temperature range is 425–600°C, with the peak
temperature below 650°C to strike a balance between thorough devolatilization
and minimal secondary cracking of vapors. The optimum yield in vapor products
translates to the quantity of bio-oil formed. However, the peak temperature can be
up to 1000°C if gas production is of primary interest [5]. Woody biomass (poplar,
sawdust, forest and wood residue) produces the highest bio-oil yield (around
75%). The second highest bio-oil yield is from energy crops (reed), followed
by agricultural residues (wheat straw, flax straw etc.). This is due to the higher
cellulose and hemicellulose in wood than energy crops and agricultural residues.
Product (bio-oil, biochar and syngas) yields in fast pyrolysis are affected by the
feed particle size. The heat transfer rate decreases with increasing particle size,
thus, increasing biochar yield and decreasing bio-oil and syngas yield. Smaller
particle size is better for internal heat transfer, which increases bio-oil yield. Both
pyrolysis temperature and feedstock particle size need to be optimized for maxi-
mum bio-oil yield [56, 80].
A finely ground biomass feed (usually <1 mm) is required to achieve very high
heat transfer rates and thereby very high heating rates, which reduce the mass
and heat transfer limitations. The biochar yield in fast pyrolysis is generally low
as only primary char is being produced (secondary reactions are suppressed) and
high reaction rates also minimize biochar formation. The overall fast pyrolysis
process is highly endothermic due to the absence of secondary reactions. Fast
pyrolysis prefers biomass with low moisture content (< 10 wt%) in order to
minimize the water in the product bio-oil. Low moisture content also facilitates
grinding the feed to give sufficiently small particles to ensure rapid heating and
fast pyrolysis [65].

5.3.5 Flash pyrolysis

Flash pyrolysis aims to maximize the liquid yield (bio-oil). It is characterized by

high temperatures, higher heating rates (> 1000°C/s) and shorter residence times
(< 0.5 s). Very fine particles of biomass feed (< 0.2 mm) are usually required. Flash
pyrolysis is extremely fast, thus, leading to a reduced time for processing of the
feedstock. It occurs in the temperature range of 800–1000°C [77]. The product con-
taining condensable and non-condensable gas is cooled, thus increasing the liquid
yield while reducing biochar production. The main product distributions of flash
pyrolysis are similar to that of fast pyrolysis. The small particle sizes of biomass feed
result in small particles of biochar. The liquid (bio-oil) yield is typically 75–80 wt%
and biochar yield is 12–13 wt%. Biochar particles need to be removed because it can
catalyze the polymerization of some of the products and increase bio-oil viscosity.
Special reactors, such as appropriately designed fluidized bed or entrained flow
reactors, are typically required [21].

5.3.6 Microwave-assisted pyrolysis

In conventional heating, heat is transferred to the material surface (by convec-

tion, conduction and radiation) and subsequently from the surface to the interior
of the material by conduction as a result of temperature gradients. On the other
hand, microwave energy is delivered directly into materials within an electromag-
netic field. The electromagnetic field enters the material and generates thermal
energy throughout the penetration depth by dielectric heating through interac-
tion with polarizable dipoles present in the material and heat the material from

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inside. Microwave heating requires a material with a high dielectric constant. The
dielectric constant is a measure of the ability of a material to absorb microwave
energy. Biomass has a relatively low dielectric constant. As a result, microwave
pyrolysis requires catalysts as well as microwave absorbers to improve the heat-
ing. The presence of water in biomass may increase the heating rate of microwave
pyrolysis due to the high dielectric constant of water in comparison with bio-
mass. Microwave-assisted pyrolysis usually operates in the temperature range of
400–800°C [72, 81].
Some of the advantages of microwave-assisted pyrolysis over conventional
pyrolysis include uniform heating throughout, rapid heating rate, cleaner products
due to no agitation, volumetric and selective heating. Microwave heating provides
ease of operation by instant on/off control and improves the yield and quality of the
products. It reduces the formation of hazardous products and minimizes pollut-
ants emission, making the technique environmentally friendly [72, 81]. The other
advantages include high heating efficiency as heating is in situ, the ability to handle
wet biomass without drying and the ability to pyrolyse large biomass particles. The
disadvantage of microwave-assisted pyrolysis is that it requires electricity which is
expensive high-quality energy compared to the heat generated by the combustion of
pyrolysis gases and vapors in conventional pyrolysis. Microwave pyrolysis generally
needed pre-treatment and catalysts before heating [21].

5.4 Hydrothermal processing

Most biomass materials are wet and have moisture contents range up to
95 wt%. Biomass with more than 30 wt% moisture content requires energy costly
drying operation prior to pyrolysis, which is one of the leading technical barriers
in using wet biomass. For high moisture content biomass, the heat of moisture
evaporation is greater than the heat available from the biomass, thus becoming a
net energy consumption. Wet biomass, typically with 70 wt% or more water, can
be converted using hydrothermal processing, which involves applying heat and
pressure to convert biomass in the presence of water into carbonaceous biofuel.
In hydrothermal processing, water plays an active role as a solvent and reactant. It
uses subcritical or supercritical water to convert biomass into end products in the
absence of atmospheric oxygen. Hydrothermal processing is a promising tech-
nique to convert wet biomass into carbonaceous solids at relatively high yields by
omitting the energy-intensive drying before or during the process. Hydrothermal
processing can be classified into three processes: hydrothermal carbonization
(HTC), hydrothermal liquefaction (HTL) and hydrothermal gasification (HTG)
based on reaction parameters such as temperature, pressure and residence
time [21].

5.4.1 Hydrothermal carbonization

When biomass feedstock in water is heated at low temperatures (< 200°C) in a

sealed vessel at autogenous pressure, mostly solids (called hydrochar) are formed in
a process known as HTC. The decomposition temperature of hemicellulose is usu-
ally around 160°C in subcritical water, while cellulose and lignin decompose in the
temperature range 180 to 200°C and above 220°C in subcritical water, respectively.
The three products of HTC are hydrochar (solid fraction), aqueous solution (bio-oil
mixed with water) and a small volume of gas (mainly CO2). HTC aims to maximize
the yield of hydrochar. The product distribution and characteristics will mostly
depend on three factors: type of biomass, the pH and the maximum temperature
used. The reaction time and the solids concentration in biomass water mixture

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also has a relatively smaller influence. A minimum HTC temperature of 160°C is

needed for the hydrochar formation from glucose. The overall HTC reaction extent
is negligible below these processing conditions. The maximum hydrochar yield is
obtained at 200°C and then it decreases gradually. A decreasing trend of hydrochar
formation with the increase in temperature is due to the higher temperatures favor-
ing gasification reactions. Consequently, part of hydrochar is lost in the formation
of volatile compounds. The process energy requirements and final product com-
position depend on the input biomass feed and the process conditions. The main
product of HTC is hydrochar which can be easily separated from the liquid fraction
due to its high hydrophobicity and homogeneous properties. The solid fraction can
be used to produce dried hydrochar pellets for energy production and mono sugars
can be recovered from the liquid fraction. HTC generates less harmful gases such as
CO and CO2 and produces hydrochar mass yields varying from 35% up to 80%, with
hydrochar carbon content similar to lignite. Residence time varies from minutes up
to several hours [21, 70, 82, 83].

5.4.2 Hydrothermal liquefaction (HTL)

At elevated temperatures (between 200 and 350°C) and pressures (5–20 MPa),
HTL takes place and the biomass feedstock is mainly converted into a liquid product
(aqueous soluble). Free radical and ionic reactions are considered to be the main
reactions in HTL [21, 84]. The dielectric constant of water decreases rapidly with
increasing temperature. At ambient conditions, the dielectric constant (a measure
of hydrogen bonding) of water is about 80 F/m. It drops to about 27 F/m at 250°C
and 5 MPa and to about 14 F/m at 350°C and 25 MPa. Water starts to display less
polar behavior due to decreasing number of hydrogen bonds. The dissociation of
water also increases with the increase of temperature. The ionic product of water
(pKw) decreases from 14 at 25°C to 11 at 250°C. The viscosity of water decreases
with increasing temperature. Thus, mass transfer is enhanced and any mass-trans-
fer-limited chemical reactions are accelerated [84, 85].

5.4.3 Hydrothermal gasification (HTG)

HTG operates near and/or above the critical point of water at temperatures of
400–600°C and pressures of 23–45 MPa. The biomass is mainly converted into a
mixture of non-condensable gases (H2, CO, CH4 and CO2). HTG is capable of pro-
ducing syngas enriched with H2. The conversion efficiency is highly improved when
water reaches the critical point (374°C and 22.1 MPa) [21]. HTG involves the splitting
of biomass polysaccharides with supercritical water (SCW). Due to higher reaction
temperature, HTG progresses at a faster rate and complete decomposition of biomass
is achieved. This is a distinctive feature of HTG in comparison with other hydrother-
mal treatments (HTC and HTL). The difficulty of byproducts treatment is one of the
problems with HTC and HTL. Undesirable byproducts produced by HTC and HTL
are occasionally dissolved in the water phase. HTG typically decomposes biomass
into gas with a conversion higher than 0.8. The amount of organic compounds in the
liquid fraction is low; hence, post-treatment is unnecessary or easily carried out. HTG
usually requires wet biomass; other biomasses can also be used. Conventional thermal
gasification technologies are available when biomass is not wet. Conventional thermal
gasification cannot be effectively employed when the feedstock is wet or has a high
moisture content (> 80%). Conventional thermal gasification is achieved by partial
oxidation using air. Syngas is partially diluted with nitrogen in addition to tar produc-
tion. Syngas from HTG does not contain tars; even if produced, they remain in the
liquid phase and are not diluted with nitrogen [21, 86].

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6. Conclusions

Biomass is a sustainable source of energy. Natural biomass is bulky and usually

has a high moisture content which complicates the direct use of biomass as a fuel.
Biomass is a complex mixture of polymers consisting of three key elements carbon,
oxygen and hydrogen. In addition, there are macronutrients, micronutrients, trace
elements and other heavy metals. The three major components of LCB are cellulose,
hemicellulose and lignin. Other compounds present in LCB include inorganic
compounds and organic extractives. The components of biomass behave differently
during thermochemical conversion.
The proximate and ultimate analysis is vital for describing biomass and thus
product distribution. Thermochemical conversion is an increasingly feasible route
to use biomass sources to fulfill energy needs. Designing effective thermochemical
conversion systems that result in proper combinations of biomass feedstocks and
conversion technologies is vital. It involves the design of efficient supply chains
and conversion technologies suitable to manage variations in biomass properties.
It needs to be cost-effective while minimizing harmful emissions and maintaining
product quality.
Different thermochemical conversions of biomass are employed to yield vary-
ing amounts of gaseous, liquid and solid products of interest. Torrefaction aims to
maximize the yield of solid product, torrefied biomass. It is performed at longer
residence time, slow heating rates and low temperatures (<300°C). The improved
properties of torrefied biomass include increased energy density, hydrophobicity,
grindability and reduced biodegradability compared to the initial biomass feed,
thus, allowing cheaper transport, handling and processing of the torrefied bio-
mass. Torrefied biomass has a higher O/C ratio than biochar. Biochar is the desired
product in slow pyrolysis, and yield is maximized by conversion at longer residence
time, slow heating rates, and moderate temperatures. Biochar applications include
use as a soil amendment, as an adsorbent or as fuel in power generation. In fast
pyrolysis, bio-oil is the desired product and yield is maximized by conversion at
short vapor residence times, high heating rates and around 500°C. The gap between
biomass feedstock and a usable product can be bridged by incorporating additional
processes such as drying and grinding of biomass feed, palletization or briquetting
of biomass feed and/or product and mineral leaching of products to treat high ash
content. These additional processes have cost implications.
High moisture content is a major barrier in biomass handling and processing.
Moisture content has a significant impact on the biomass conversion process. The
main problem with the pyrolysis of high moisture biomass is that it requires a large
amount of energy to evaporate moisture. Hydrothermal processing is a useful pro-
cessing technique for biomass feedstocks with high moisture as it does not require
the drying and/or dewatering processes, thereby reducing the operating costs.

Acknowledgements

The authors would like to thank the Office of Applied Research, Higher Colleges
of Technology (HCT), UAE, for financial support.

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Recent Perspectives in Pyrolysis Research

Author details

Meegalla R. Chandraratne* and Asfaw G. Daful

Higher Colleges of Technology, Abu Dhabi, United Arab Emirates

*Address all correspondence to: [email protected]

© 2021 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms
of the Creative Commons Attribution License (http://creativecommons.org/licenses/
by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.

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DOI: http://dx.doi.org/10.5772/intechopen.100060

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