Renewable Energy 129 (2018) 695e716

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

A comprehensive review on the pyrolysis of lignocellulosic biomass

Vaibhav Dhyani a, Thallada Bhaskar a, b, *
a
Thermo-catalytic Processes Area (TPA), Bio-Fuels Division (BFD), CSIR-Indian Institute of Petroleum (IIP), Dehradun 248005, India
b
Academy of Scientific and Innovative Research (AcSIR), India

a r t i c l e i n f o a b s t r a c t

Article history: In the pursuit of renewable sources of energy, biomass is emerging as a promising resource because of its
Received 15 February 2017 abundance and carbon neutral nature. Pyrolysis is a prevailing technology for biomass conversion into
Received in revised form the valuable hydrocarbon and alternative fuels. In this review, pyrolysis of lignocellulosic biomass has
14 April 2017
been addressed, focusing primarily on the ideal feedstock, technologies, reactors, and properties of the
Accepted 16 April 2017
Available online 18 April 2017
end product. Technical problems in using biofuel from pyrolysis, as transport fuel have also been dis-
cussed, along with solutions to address these challenges, and comments on the future scope of the
pyrolysis process.
Keywords:
Pyrolysis
© 2017 Elsevier Ltd. All rights reserved.
Lignocellulosic
Biomass
Feedstock
Reactors

1. Introduction hectare per year [2]. Lignocellulosic biomass can be utilized in

With the depleting fossil fuel resources, increasing environ-
mental concerns, and political commitment, research has been
growing in the field of alternate energy sources. The UN climate
panel has aimed for a reduction in greenhouse gas emission by
50e80% by 2050 [1]. To realize this target, it is essential to shift the
dependency from fossil fuels to the renewable energy sources. The
renewable resources are inherently conceived using the energy
present in sunlight and its direct and indirect impacts on the Earth
(falling water, heating effects, photons, plant growth, wind, etc.),
gravitational forces (the tides), and the heat of the Earth's core
(geothermal). These resources represent a gigantic underexploited
capital of energy, which can meet much of the growing energy
demand at prices less than those of conventional fossil fuels if
provided adequate support.
Biomass is the generic term for the plant (phytomass) and ani-
mal (zoomass) biomass. Lignocellulosic biomass refers to dry plant
matter, which is an abundant and low-cost source of renewable
energy. It is significantly cheaper than the conventional fuel on an
energy basis. On agricultural land, the growth rate of lignocellulosic
biomass on a per energy basis is 30e240 Barrel of oil equivalent per
* Corresponding author. Thermo-catalytic Processes Area (TPA), Bio-Fuels Divi-
sion (BFD), CSIR-Indian Institute of Petroleum (IIP), Dehradun 248005, India.
E-mail address: tbhaskar@iip.res.in (T. Bhaskar).
following the ways to procure energy:
(a) Direct combustion to produce heat. The heat generated by
this method must be exploited immediately for heating or
power generation. Other than the obvious problem of low
efficiency, this approach also leads to undesirable ash
buildup. The huge amount of CO2, produced as a by-product
of combustion is also a significant disadvantage.
(b) Conversion of biomass into biofuels and valuable hydrocar-
bons using thermochemical or biochemical routes.
Biofuels are the liquids or gases produced from biomass, which
can be burned for obtaining energy. The first generation of biofuels
comprised of biodiesel and bioethanol produced from different
biomass such as edible and non-edible crops, agricultural wastes,
and aquatic plants. The second generation of biofuels will be based
on biomass resources processed from integrated bio-refineries,
covering not only the production of biofuels, heat, and electricity,
but also biomaterials [3]. Despite having a low carbon content,
biofuels are environment-friendly, as they have negligible content
of sulfur, nitrogen, and ash; which leads to a lower emission of SO2,
NOx, and soot, compared to conventional fossil fuels [4]. Moreover,
the CO2 released during the combustion of biofuels is taken up by
plants for photosynthesis, thus balancing the CO2 cycle [5].
‘Thermochemical processing’ of biomass uses heat and catalysts
to transform plant polymers into biofuels and other useful

http://dx.doi.org/10.1016/j.renene.2017.04.035
0960-1481/© 2017 Elsevier Ltd. All rights reserved.
696 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716
chemicals. This contrasts with the ‘biochemical processing’ of
biomass, which uses enzymes and microorganisms for the same
purpose. Biomass conversion via biochemical route is often
considered as ‘mature’ technology with little scope for improve-
ment [6]. In comparison with biochemical processes, thermo-
chemical processes occur faster (in a few seconds to hours);
whereas the former takes time (in the range of days) to complete.
Also, unlike the biochemical processes, which produce lignin as a
by-product and face difficulty in fermenting the C5 sugars, ther-
mochemical methods of conversion utilize the whole feedstock to
produce value-added hydrocarbons. Another advantage of ther-
mochemical methods of conversion is that they are not feedstock
specific and can even process the combinations of feedstocks.
Gasification and pyrolysis are two of the most researched pro-
cesses for thermochemical biomass conversion. Gasification pro-
vides fuel gas that can be combusted for heat generation, while
pyrolysis yields a liquid fuel that can substitute for fuel oil in any
static heating or electricity generation application. Pyrolysis is
thermal decomposition of a feed substance into smaller fragments
by heating in the absence of oxygen. The main benefit of pyrolysis
process over gasification is that the liquid fuel produced can be
easily stored and transported.
Conversion of solid biomass to liquid fuel is desirable as it in-
creases the volumetric heat content, decreases the cost of trans-
portation, and also enables them to be used in existing equipment
(oil boilers, etc.). Although the thermal decomposition of organic
materials for the production of valuable liquid hydrocarbons, has
been investigated since centuries, the interest in pyrolysis for
production of biofuels emerged less than 40 years back [7].
Different reactor configurations such as vortex reactor, rotating
blade reactor, rotating cone reactor, vacuum reactor, and bubbling
and circulating fluidized bed reactors were explored in 80's and
90's. This resulted in the establishment of pilot plants in late 90's in
Spain, Italy, UK, Canada, Finland, and Netherland [8].
In this review article, a thorough comprehension has been
presented on the pyrolysis process as a paramount thermochemical
biomass conversion technique. Lignocellulosic biomass, which is an
ideally suited feedstock for pyrolysis has been discussed, for its
composition, categorization, and characterization. Different kinds
of pyrolysis and reactor configurations to execute them have been
addressed in the subsequent sections. The product distribution,
Fig. 1. Components of lignocellulosic biomass: (a) cellulose, (b) structure monomers of hemicellulose, and (c) lignin.
along with its analysis has also been addressed in the later sections,
with more stress being laid on bio-oil and its upgradation. Since
pyrolysis is still in its developing stage, many challenges stand in
the way of substantial implementation of the process. However,
each challenge provides a room for improvement and an oppor-
tunity for advancement. These challenges have been presented in
the last sections of this article, along with potential solutions that
will determine the fate of pyrolysis.
It has been the best interest of the authors to embed this article
with references to the valuable research work, which have been
done in the field of pyrolysis of lignocellulosic biomass.
2. Lignocellulosic biomass
Lignocellulosic biomass is typically composed of three main
building blocks: cellulose, hemicellulose, and lignin.
2.1. Cellulose
Cellulose (Fig. 1(a)) is the most abundant organic polymer,
present in the cell wall of the plant cells; and almost in the pure
form in the cotton fibers. It is a natural polymer of repeating D-
glucose units, a six-carbon ring, also known as pyranose. The three
hydroxyl groups in each pyranose ring can interact with one
another forming intra- and intermolecular hydrogen bonds which
give cellulose a crystalline structure, and its unique properties of
mechanical strength and chemical stability. The pyranose rings are
linked to each other by acetal bonds (eOe, b-1,4-glycoside linkage)
between C-1 of one pyranose ring and C-4 of the succeeding ring.
Since a molecule of water is lost in such linkage, cellulose can also
be defined as a polysaccharide of anhydroglucopyranose [9].
2.2. Hemicellulose
Hemicellulose (Fig. 1(b)) surrounds the cellulose fibers and
stands as a connecting link between cellulose and lignin. It is a
heterogeneous group of branched polysaccharides. Different
monomers such as glucose, galactose, mannose, xylose, arabinose
and glucuronic acid, are the structural elements of hemicellulose.
The degree of polymerization (DP) of hemicellulose is 50e200
monomers, which is much lower than that of cellulose [10]. While
 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716
cellulose has a hydrolysis-resistant crystalline structure, hemi-
cellulose is amorphous, with little physical strength. It is readily
hydrolyzed by dilute acids or bases, as well as hemicellulose
enzymes.
2.3. Lignin
Lignin (Fig. 1(c)) is an aromatic, three-dimensional and cross-
linked phenol polymer that consists of a random assortment of
differently bonded “hydroxyl-” and “methoxy-” substituted
phenylpropane units. These phenylpropane monomers can be
categorized as guaiacyl, syringyl and p-hydroxylphenyl units
[11,12]. Lignin is mainly present in the outer layer of the fibers
and is responsible for the structural rigidity, and holding the fi-
bers of polysaccharides together. Lignin percentage may vary
from 23 to 33% in softwoods to 16e25% in hardwoods. For the
lignocellulosic biomass, lignin percentage up to 40% has been
reported. Physically, cellulose microfibrils are coated with
hemicellulose, whose empty spaces are filled up with lignin [13].
Lignin plays a binding role between hemicellulose and cellulose
within the cell wall.
The specific structure of lignin varies with the parent biomass
and may also show differences based on the extraction method.
Softwood and hardwood lignin have dissimilar structures.
“Guaiacyl” lignin, which is predominantly found in softwoods, is a
polymer of higher fraction of coniferyl phenylpropane units. On the
other hand, “Guaiacyl-syringyl” lignin, which is typically found in
hardwoods, is a copolymer of both the coniferyl and sinapyl phe-
nylpropane units. The fraction of sinapyl units in hardwoods is
higher than that in softwood lignin [14,15]. Due to the presence of
both guaiacyl and syringyl units, the hardwood lignin has higher
methoxyl content, compared to the softwood lignin, which is
composed of guaiacyl units only [16].
Other than these three components, biomass also comprises of
some extractives and inorganic components. Extractives include
alkaloids, essential oils, fats, glycosides, gums, mucilages, pectins,
phenolics, proteins, resins, saponins, simple sugars, starches, ter-
penes, and waxes. These can be extracted from biomass using polar
(alcohol, methylene chloride, or water) or nonpolar solvents (hex-
ane or toluene). Extractives function as intermediates in meta-
bolism, as energy reserves, and as plant defenses against microbial
and insect attack [15]. The inorganic components are present as ash
in the biomass and are addressed in section 4.4.
3. Feedstock for pyrolysis
The availability of industrial quantities of lignocellulosic
biomass is a necessity for the establishment of any biorefinery. An
abundant supply of renewable feedstock is globally available for
being converted into biofuels, such as agricultural crops, residues,
forestry materials, and algal biomass. Dedicated energy crops such
as sorghum and several varieties of grasses; and municipal solid
waste (MSW) are also attracting attention. As per a macro level
study in the US alone, the annual supply potential of dry agricul-
tural and forest biomass is 900 and 400 million tons respectively,
which is sufficient to replace more than 30% of the current trans-
port fuel use [17]. However, not all biomass are suitable for being
converted into liquid fuels and appropriate selection of feedstock
for thermochemical conversion is necessary for process optimiza-
tion. Ganesh [18] developed criteria for evaluating the suitability of
biomass for a conversion process to obtain solid, liquid and gaseous
fuels. In his method, the Rating Indices (RI) of different biomass
were calculated using the yield, HHV, and ultimate analysis data.
These RI allowed the ranking of the tested biomass for gasification,
carbonization and liquefaction operations.
697
3.1. Wood biomass
Various kinds of wood-based biomass have been used for py-
rolysis. Different softwoods that have been studied include cedar
[19], douglas fir [20], pine [21,22], redwood [23], and spruce [21,24].
The hardwood varieties that have been majorly studied are bald
cypress [25], beech [23,26], birch [27,28], blackbutt [29], chestnut
[23], eucalyptus [19], hybrid poplar [30,31], and oak [19,32]. Wood
waste including sawdust [33,34], particle board [35], waste from
furniture factories and other wood processing industries [36] has
also been studied by several research groups.
3.2. Agricultural waste
Pyrolysis of agricultural waste is desirable, as the cultivation of
agricultural crops has less demand of area and cultivation period,
compared to wood biomass. Also, a large part of the crop body is
non-edible and goes as waste. Straw makes up as much as 50% of
the yield of cereal crops and has more potential for char production
compared to wood [37].
Different varieties of agricultural wastes that have been tested
for pyrolysis include ‘shells’ (cotton cocoon [38,39], almond [40,41],
ground nut [42], hazelnut [43e45], nut [40], oil palm [46], etc.),
husks (olive [39,47], rice [48,49], etc.), ‘stover’ (corn [30]), ‘stalk’
(corn [50], cotton [51], rape [52], etc.), ‘straws’ (corn [50], cotton
[51], rape [52], wheat [50], etc.), and ‘non-edible seeds’ (babool
[53], grape [40], karanja [54], linseed [54], mahua [54], niger [54],
rape [55,56], etc.). Pyrolysis of other agricultural wastes, like apricot
stones [40], bagasse [27,57], banana leaves [58], bocaiuva residues
[59], cherry stones [40], coir pith [12], cotton seed cake [60,61],
garlic stem [62], grape residue [47], jatropa residue [63,64], jute
sticks [65], olive waste [66,67], pepper stem [62], safflower seeds,
sorghum bagasse [68], sunflower bagasse [69], tea waste [39], and
tobacco waste [68], has also been reported in literature.
One of the major concerns with use of agricultural residue as
feedstock for pyrolysis is that farmers and landowners control the
supply of biomass. Not only is the bulky agricultural residue limited
to a local market due to transport costs, the composition of feed-
stock is also inconsistent and variable. The feedstock from farms is
also susceptible to dirt in the biomass, which can lead to equipment
wear and increased maintenance cost [70].
3.3. Energy crops
Certain crops of high energy values, such as bamboo [71], sor-
ghum [72] and many varieties of grasses have also been studied for
pyrolysis. Energy crops cut the competition for fertile land as they
can be grown on land that is not suitable for agricultural crops.
Bamboo is a class of more than 1250 species of fast growing, large
woody grasses, found abundant in Asia. Lignin content as high as
29% has been reported in some of the bamboo species [73].
Sorghum is a genus of grasses found in parts of Asia and Africa.
Raw sweet sorghum comprises of 14e16% lignin on a dry basis. It is
of interest as a dedicated agricultural energy crop because of its
drought tolerance, relatively low input requirements (water and
manure), and ability to produce high yields under a wide range of
environmental conditions. Sweet sorghum comprises of large sugar
content in the crop that can be converted to ethanol, while the
bagasse can be easily used a feedstock for thermochemical con-
version processes [72].
Grasses are usually rich in hemicellulose. Typical grasses may
comprise of 25e40% cellulose, 35e50% hemicellulose and 10e30%
lignin [74]. Several genus of grass family such as bermuda grass,
elephant grass, esparto grass, switch grass [30,75] etc. have been
used as feedstock for pyrolysis by different researchers. Parrish and
698 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716
Fike [76] mentioned that switchgrass can be grown on soils of
moderate fertility without fertilizing, or with limited additions of
fertilizer, and still maintain productivity.
Use of dedicated energy crop as a feedstock will require change
in current production and crop management practices. A reliable
market will be needed for the farmer to commit to producing such
biomass.
Other than the above mentioned biomass, pyrolysis of feedstock
such as aquatic biomass [77e81], cattle manure [82], household
waste [83,84], municipal solid waste [84,85], oil shale [86], poultry
litter [87], sewage sludge [24] and used oils [88] has also been re-
ported in literature.
4. Feedstock analysis
Analysis of biomass is an imperative step in order to assess its
value as feedstock for pyrolysis, determining the reaction condi-
tions, and predicting the product behavior.
4.1. Proximate analysis
The simplest and most commonly used analysis technique is
proximate analysis. Proximate analysis is performed to determine
the four essential feedstock fractions: (a) moisture, (b) volatile
matter, consisting of the components of biomass, except for water,
which are liberated as gases and vapors at high temperature in the
absence of oxygen, (c) fixed carbon, the non-volatile fraction of
biomass, and (d) ash, the inorganic residue the remains after
combustion.
Biomass with high volatile matter has highest conversion, in
comparison to biomass with high fixed carbon. Theoretically,
biomass with higher volatile fraction may be suitable for produc-
tion of bio-oil, while the one with higher fixed carbon may be more
suitable for production of bio-char. Table 1 presents the literature
survey of proximate analysis of different biomass feedstock.
4.2. Ultimate analysis
Ultimate analysis test produces more comprehensive results
than the proximate analysis. It involves determining the carbon,
hydrogen, nitrogen, sulphur and oxygen (CHNSO) in the material.
The ratio of these elements obtained from ultimate analysis provide
a better comparison among the feedstock. The results can also be
used for determination of heating value of the feedstock. Chaniwala
and Parikh [89] developed following empirical correlation for
determination of higher heating value (HHV) of the biomass using
the elemental and proximate analysis:
HHV, MJ/kg ¼ 0.3491(C) þ 1.1783(H) e 0.10(S) e 0.0134(O) e
0.0151(N) e 0.0211(A) (1)
Friedl et al. [90] provided two correlations for calculation of
HHV based on the data of ultimate analysis: an ordinary least
squares regression (OLS) (Eq. (2)) and a partial least squares
regression (PLS) method (Eq. (3)). These equations were calibrated
using 122 different biomass samples and give the HHV on a dry
basis.
HHV, MJ/kg ¼ 1.87(C2) e 144(C) e
2802(H) þ 63.8(CH) þ 129(N) þ 20147 (2)
HHV, MJ/kg ¼ 5.22(C2) e 319(C) e
1647(H) þ 38.6(CH) þ 133(N) þ 21028 (3)
Gaur and Reed [91] have published the proximate and ultimate
analysis data of about 300 biomass samples in their handbook
“Thermal Data for Natural and Synthetic Fuels”.
4.3. Fiber analysis
The quantity of individual lignocellulosic fractions in a biomass
sample can be found by numerous wet chemical analytical
methods via determination of Neutral Detergent Fiber (NDF), Acid
Detergent Fiber (ADF) and Acid Detergent Lignin (ADL) [92e94].
These analytical procedures are standardized by the American So-
ciety for Testing and Materials (ASTM) and the Technical Associa-
tion of the Pulp and Paper Industry (TAPPI). NDF is obtained by
stripping the starch and extractives from the biomass sample,
leaving cellulose, hemicellulose and lignin. ADF is obtained by
removal of hemicellulose from the sample. On removal of cellulose
from ADF, ADL is obtained. The values of hemicellulose and cellu-
lose are obtained by difference in the values of NDF, ADF and ADL
[95]. Table 1 presents the lignocellulosic composition, as well as
proximate and ultimate analysis of different biomass as reported in
the literature.
The ratio of the three constituents, depend on the nature of
biomass and the part of the plant being sampled. For example,
hazelnut shell contains up to 51.3% lignin [96] while tree leaves are
lignin-free [97]. Lignin content in cotton cocoon shell is 48.7% [98],
while its seed hair has no lignin [12].
4.4. Inorganic metals in feedstock
Inorganics compounds are present as ash in the biomass feed-
stock. The main inorganic constituents being compounds of po-
tassium, calcium, sodium, silicon, phosphorus, and chlorines.
Inductively coupled plasma mass spectrometry (ICP-MS), and
inductively coupled plasma atomic/optical emission spectroscopy
(ICP-AES/OES) are commonly used techniques reported in literature
for determination of inorganic content in biomass. Table 2 presents
the literature survey of the elemental analysis of inorganics in some
of the biomass feedstock.
The composition of ash in bio-mass ranges from less than 2% in
softwoods to as much as 15% in herbaceous biomass and agricul-
tural residues (see Table 1).
4.5. Thermal analysis
Along with feedstock composition, knowledge of feedstock
decomposition behavior is also important for design of a pyrolysis
process. The decomposition behavior of the biomass is studied
using thermal analysis, the commonly used techniques for which
involve, thermogravimetric analysis and differential scanning
calorimetry.
Thermogravimetric analysis (TGA) is a technique in which
weight loss of a sample is measured with increasing temperature.
TGA data can be used for, (1) material analysis by comparison with
characteristic decomposition patters, (2) formulation of reaction
kinetics, (3) proximate analysis, (4) analysis of thermal stability, etc
[124]. Carrier el al [95] demonstrated the use to TGA for determi-
nation of lignocellulosic composition of biomass.
Fig. 2(a), shows TGA curves of pure cellulose, hemicellulose and
lignin samples. It can be observed that the three biopolymers
decompose at distinct temperature spectrums. Hemicellulose starts
an early decomposition, with most decomposition taking place in
the temperature range of 220e315  C. Decomposition of cellulose is
mainly confined in the temperature range of 315e400  C, with very
less solid residue remaining after 400  C. Among the three com-
ponents, lignin is the most difficult one to decompose. Its decom-
position occurs slowly under a wide range of temperature from
Table 1
Lignocellulosic and ash composition of different biomass from literature.

Feedstock Fiber Analysis, % Proximate Analysis, % Ultimate Analysis, % HHV, MJ/kg Ref.

Cellulose Hemicellulose Lignin Moisture Volatile matter Fixed Carbon Ash C H N S O

Wood based biomass

Ailanthus wood 46.7 26.6 26.2 8.1 73.5 24.8 0.5e1.7 49.5 6.2 0.3 e 41.0 19.0 [96]
Albizia 59.5 6.7 33.8 9.7 72.7 25.5 1.8 46.4 5.8 0.6 1.7 45.5 17.4 [99]
Beech wood 45.8 31.8 21.9 9.7 85.9 13.4 0.4e0.7 46.9 6.2 0.3 0.7 45.9 18.7 [100]
Birchwood 25.7 40 15.7 11.13 78.7 20.9 0.3 48.4 5.6 0.2 e 45.8 e [37,101]
Furniture sawdust 32.63 37.23 22.16 7.1 79.43 12.69 0.78 47.42 5.67 0.2 e 46.71 15.79 [102]
Furniture sawdust 37.23 32.63 22.16 7.1 79.43 12.69 0.78 47.42 5.67 0.20 e 46.71 15.79 [102]
Hardwood (av.) 45.2 31.3 21.7 7.8 72.3 25.0 2.7 48.6 6.2 0.4 e 41.1 18.8 [96]
Iroko e e 26.2 9.4 70.4 26.1 3.5 43.90 5.3 0.4 3.5 46.90 16.5 [100]
Oak 43.2 21.9 35.4 0.6 89.7 9.5 0.2 e e e e e e [103]
Pine 45.6 24.0 26.8 0.5 88.1 10.3 1.1 e e e e e e [103]
Softwood (av.) 45.8 24.4 28.0 8.8 70.0 28.1 1.7 52.1 6.1 0.2 e 41.0 20.0 [96]
Spruce wood 50.8 21.2 27.5 8.4 83.5 16.1 0.5 48.3 6.3 0.4 0.4 44.6 19.5 [100]
Subabul wood 39.8 24.0 24.7 e 85.6 e 0.9 48.2 5.9 0.0 e 45.1 19.78 [42]
Wood bark 22 47 31 8.8 66.6 31.8 1.6 53.1 6.1 0.2 40.6 20.5 [96,97]

V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716

e
Wood chips 31.8 31.8 19.0 7.30 82.29 10.15 0.26e0.45 46.4 5.9 0.085 e 47.62 20.34 [47,104]
Agricultural waste
Almond shell 29.0e31.1 28.0e38.0 27.7e35 8.7 79.7 4.9 2.3 54.7 7.5 0.3 0.3 37.4 20.2 [105]
Babool seeds e e e 12.5 69.1 11.0 7.3 54.1 6.12 5.23 e 34.53 e [53]
Bagasse 41.3 22.6 18.3 e 84.2 e 2.9 43.8 5.8 0.4 e 47.1 14.67 [42]
Banana waste 13.2 14.8 14 7.8 78.2 15.6 11.4 43.5 6.2 0.86 0.95 42.3 17.1 [58]
Barley straw 48.6 29.7 27.7 6.9 78.5 4.8 5e9.8 41.4 6.2 0.63 0.01 51.7 15.7 [106]
Cashewnut shell 41.3 18.6 40.1 10.43 69.31 19.26 1.00 e [107]
Coconut coir 47.7 25.9 17.8 e 82.8 e 0.8 47.6 5.7 0.2 e 45.6 4.67 [42]
Coconut shell 36.3 25.1 28.7 e 8.02 e 0.7 50.2 5.7 0.0 e 43.4 20.50 [42]
Coir pith 28.6 15.3 31.2 e 73.3 e 7.1 44.0 4.7 0.7 e 43.4 18.07 [42]
Corn cob 40.3e45 28.7e35 15e16.6 9.7 80.6 18.2 1.2e2.8 43.6 5.8 0.7 1.3 48.6 16.9 [40,100]
Corn stalk 22.82 43.01 15.59 e e e 7.44 43.83 5.75 0.97 0.13 48.94 e [108]
Corn stover 51.2 30.7 14.4 10.6 78.7 17.6 3.7 e e e e e 17.8 [96]
Cotton cocoon shell 32.6 18.7 48.7 e e e 5.8 e e e e e e [98]
Cotton gin waste 77.8 16.0 0.0 e 88.0 e 5.4 42.7 6.0 0.1 e 49.5 17.48 [42]
Cotton seed hair 77e95 5e20 0 e e e 5.4 e e e e e e [12,97]
Flax straw 36.70 34.40 28.90 7.9 80.3 8.8 3.0 43.10 6.20 0.68 0.09 49.90 17.00 [106]
Grape marc e e e 60 28.8 9.8 1.4 43.21 5.94 0.65 1.24 45.50 20.05 [109]
Grape residues 17.2 17.2 30.4 e e e 5.1 e e e e e e [47]
Groundnut shell 35.7 18.7 30.2 e 83.0 e 5.9 51.0 5.4 1.3 e 42.30 18.65 [42]
Hazelnut seedcoat 29.6 15.7 53.0 6.8 71.20 27.0 1.8 52.90 5.6 1.4 e 42.7 19.3 [96]
Hazelnut shell 22.9 15.7 51.5 9.0 69.3 28.3 4.3 52.30 6.50 5.20 9.2 26.8 19.3 [96,110]
Jatropa deoiled cake 53.5 16.6 24.9 0.44 79.20 18.86 1.5 42.7 6.0 0.1 e 33.0 e [63]
Millet husk 33.3 26.9 14.0 e 80.7 e 18.1 e e e e e 17.48 [42]
Nut shells 25e30 25e30 30e40 e e e 3.8 e e e e e e [40,97]
Oat straw 31e37 27e39 16e19 e e e 6e8 50.0 6.2 1.6 e 42.2 e [111]
Olive husk 18.5 18.5 28.0 9.2 70.3 26.1 2.8e3.6 e e e e e 19.0 [47,96]
Olive stones 31.8 32.7 30.0 10.2 70.5 17.2 2.1 e e e e e 20.0 [41,105]
Palm kernel shell e e e e 77.5 20.3 e 38.9 5.1 0.6 e 32.0 16.3 [112]
Rapeseed e e e 8.4 70.0 15.8 5.8 41.1 6.0 5.1 e 47.8 19.4 [113]
Rice husk 31.3 24.3 14.3 e 81.6 e 23.5 36.9 5.0 0.4 e 37.9 15.29 [42]
Rice straw 37.0 22.7 13.6 e 80.2 e 19.8 e e e e e 16.78 [42]
Rye straw 33e35 27e30 16e19 e e e 2e5 e e e e e e [111]
Sorghum bagasse 41.0 24.0 10.0 e e e 9.5 e e e e e e [68]
Sugar cane bagasse 32e44 27e32 19e24 8.5 84.00 1.64 4.5e9 45.13 6.05 0.3 e 42.77 18.17 [114]
Tea waste 30.2 19.9 40.0 6.5 85.0 13.6 1.4 e e e e e 17.1 [96]
Tobacco leaf 36.3 34.4 12.1 8.4 72.6 11.2 17.2 e e e e e 15.0 [96]
Tobacco stalk 42.4 28.2 27.0 8.9 79.6 18.0 2.4 e e e e e 17.7 [96]

699
(continued on next page)
 700 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716

ambient to 900  C. Also highest solid residue is left after pyrolysis

[111,116]

[75,115]
[96,97]
of lignin. The differences in the molecular structures and chemical

[111]
[115]

[117]

[118]
[111]

[106]
[119]
[118]

[120]
[121]
[122]
nature of the three components account for the dissimilar be-
[68]

[97]
[12]

[97]
[97]

[96]
Ref.

[2]
haviors observed [125]. The TGA patters of the lignocellulosic
biomass can be stated as convolution of the TGA curves of the
HHV, MJ/kg

three main components, with the extent of convolution depend-

ing on the percentage composition of individual components.

24.981
17.10

17.82

15.61

16.70

17.10
DSC is one of the accepted techniques used to determine the
19.1

19.5

18.8

6.56
20

11
e

e
e

e
e

e
e

e
heat flow through the sample with respect to temperature. This
method offers the heat flow profile due to the difference in the
36.10

37.40

43.56

47.43

50.40
42.96

16.22

61.70
amount of heat required to increase or decrease the temperature
34.1

31.8

39.4
37.6
37.3

39.5

39.9

45.3
e

e
e

e
O

of a sample and with respect to a reference. DSC analysis provides

quantitative and qualitative information about physical and
0.26

0.03

0.15

0.55

0.71
chemical changes that involve endothermic or exothermic pro-
0.0
e
e

e
e

e
e
e
e

e
e

e
e

e
S

cesses. Bry
s et al. [126] used DSC to provide detailed information

on change in water content of woody biomass occurring on heat
3.00

0.32

0.86

1.75

1.03
0.36

1.20

2.51
treatment. He et al. [127] used DSC for investigation of caloric
1.8

1.4

0.8
0.4
0.3

0.5

0.2

0.7
e

e
e

e
N

requirement of biomass pyrolysis using TG-DSC analysis. Fig. 2(b)

Ultimate Analysis, %

shows typical DSC curves for individual biomass components. The

7.00

5.36

6.44

5.78

6.96

1.74

4.41
5.70
5.1

5.4

5.7
5.9
6.8

5.5
6.0

6.5

thermal decomposition peaks are endothermic for volatilization

e

e
e

e
H

and exothermic for char formation. Yang et al. [125] studied the
thermal decomposition of cellulose, hemicellulose and lignin us-
53.90

45.88

46.94

45.04

12.79

30.67
48.30
45.5

44.5

48.3
56.1
48.6

48.6
42.4
48.7
49.9

ing DSC and concluded that the exothermic peaks in the decom-
e

e
e

e
C

position pattern of hemicellulose and lignin can be attributed to

their high charring nature, which is in contrast with the thermal
5.5e13.5

decomposition of cellulose taking place by full volatilization.

1.7e5

2.2e8

67.50

39.37
17.0

4.92

4.54
Ash

6.0

5.5
6.0

1.1

6.3

4.5
e

e
e

e
e

4.6. Kinetic analysis

Fixed Carbon

Kinetic study of biomass pyrolysis is essential to understand

the course of decomposition-reaction progression and for deter-
23.50

15.30

14.66

12.54

mining the dependence of the rate of progression on process pa-

16.8

12.1

16.0

17.3

3.49

5.63
16.8

rameters. The knowledge of kinetic parameters, activation energy,

e

e
e

e
e
e

e
e

pre-exponential factor and reaction model, of thermal degrada-

tion is necessary for design and optimization of pyrolysis reactors,
Volatile matter

prediction of material lifetime, CFD modeling [128], and the

establishment of process conditions. For the complex biomass
Proximate Analysis, %

73.92

77.90
78.57

29.01

53.62

mixtures, where nature of reaction changes with reaction pro-

63.0

80.5

82.5

87.6

78.7
65

gression, “Isoconversional Methods” are ideally suited for deter-

e

e
e

e
e
e

e
e

mination of activation energy. These methods are based on the

Moisture

assumption that at a constant value of activation energy, the rate

10.04

of reaction is a function of temperature only [129,130]. Several

9.15

5.20

4.34

1.27
11.0
8.5

4.7

5.0

2.8
e

e
e

e
e
e

e
e
e
e

differential and integral methods fall under the category of iso-

conversional methods, such as Friedman method [131], Flynn-
15e16.4

Wall-Ozawa (FWO) method [132], Kissinger-Akahira-Sunose

2.7e5.7
21e31

17e19
10e30

18e30
Lignin

(KAS) equation [133], Chai and Chen method [134], and Vya-
20.4

23.9

22.0
22.9
12.0
28.9

20.0

24.7
6.4

4.7
7.6

e
0

zovkin method [129,130]. Other methods for determination of

kinetic parameters reported in literature include, distributed
Hemicellulose

activation energy model [135,136], fuzzy modeling [137], and

several other model fitting methods [138,139].
27.3e50

1.4e3.3
15e26

27e32
35e50

80e85
25e40
13.0

35.7

42.6
23.9
31.3
31.4
33.1

49.3

29.2

5. Pyrolysis
24

32

e
Fiber Analysis, %

Pyrolysis is the term given to the thermal depolymerization of

Cellulose

27.3e30

organic matter in the absence of oxygen. It is an endothermic

1.6e4.7
26e43

33e38
25e40

15e20
40e55

reaction. Van de Velden et al. [24] reported the heat requirement

30.3

29.7

45.8

38.0

14.1

50.6
25
22

40

45
e

for pyrolysis of several agricultural and wood-based biomass in

the range of 207e434 kJ/kg. The rapid heating of biomass in such
Costal Bermuda grass

inert atmosphere results in the production of organic vapor

Solid cattle manure
Reed canary grass
Table 1 (continued )

composed of fragments of cellulose, hemicellulose, and lignin

Willow coppice

Waste material
Other feedstock

Sewage sludge
Elephant grass
Tobacco waste

Swine manure
Timothy grass

polymers found in the biomass. These vapors can be condensed to

Orchard grass
Esparto grass
Wheat straw

Switch grass
Energy crops

Newspaper
Sabai grass
Sugar cane

give a freely flowing organic liquid, commonly known as bio-oil.

Wild reed
Feedstock

Bamboo

Grasses

The non-condensable gases leave the reaction system and can

Leaves

be used to provide heat for pyrolysis. The remaining carbon-rich

residual is left as bio-char.
 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716 701

The product distribution of the bio-oil predominantly depends

1244

11.4
200

170
on the lignocellulosic composition of the biomass [140]. Yang et al.
5.7

8.3
Zn

16

60

25

40
11
32
22
80
52

94

47

40
18
9
[125] investigated the pyrolysis characteristics of cellulose, hemi-
cellulose, and lignin individually. It was observed that the decom-
position of hemicellulose occurred at 220e315  C. Cellulose

5700
decomposed in the temperature range of 314e400  C. The
750
640

476

564

299

317
163
221

787
60

64
35

15

58

66
e

e
S

decomposition of lignin took place in a wide range of temperature

from 160 to 900  C, generating highest solid residue (40%). From an
energy viewpoint, pyrolysis of cellulose was observed to be endo-
16
10
20

13
22

13
10

11

49
32
45

25
Ni

e
2

1
thermic, while that of hemicellulose and lignin was exothermic.
The main gaseous products from pyrolyzing the three components
were similar, including CO2, CO, CH4 and some organics. The

176.4
26.5
920

170

108
463
Mn

releasing behaviors of H2 and the total gas yield were measured

9.3

27
19
12
38

44

38

25
e
e
9

4
1

2
using Micro-GC when pyrolyzing the three components in a packed
bed. It was observed that hemicellulose had higher CO2 yield, cel-
lulose generated a higher CO yield, and with a higher presence of
1239
5.1

0.5

0.0 aromatic ring and methoxyl, the cracking and deformation of lignin
Cu

18
30
60
50
68

32

11

21
e

e
e

e
5

1
7
released higher H2 and CH4. Pyrolysis of cellulose involves, the
cleavage of the glycosidic groups by dehydration, followed by a
breakdown of the “anhydroglucose” units. At lower temperatures,
0.3
0.2

11
Cr

e
e
e
e
e

e
e

e
e
e
e
e
e
e
2

the dehydration and breakdown of sugar molecules result in the

formation of char. Shafizadeh and Fu [141] reported 34.2% char
yield when pure cellulose was pyrolyzed at 300  C, in the presence
0.6
0.5
3.2

2.3
Co

e
e
e
e
e

e
e

e
e
e
e
e
e
e
8

of nitrogen. When the temperatures are high, there is sufficient

energy for rapid cleavage of glycosidic bonds and evaporation of
products, leading to the favored formation of gaseous products.
150840
220690
174510
17340

13050

13400
13000
43000
10960

44440

However, it's not just the quantitative composition of cellulose,

1200

2990

9857
256

195

hemicellulose, and lignin in the biomass, but also the interaction

30
Si

between these components that determine the product distribu-

tion in the bio-oil. It has been suggested that hemicellulose is
hydrogen-bonded to cellulose, while lignin and hemicellulose are
2000
3400

1170

2127

7200

1267
284

445

736

278

337
752

100
214
47
94

covalently bonded, more specifically, via ester bonds [142]. These

e

e
P

bonds influence the pyrolytic behavior of biomass and may cause

differences in product distribution, in comparison to a synthetically
11360

11140

prepared sample by physical mixing. Couhert et al. [143] prepared

171.5

790.5

101.3
6261
7100
4800

8095
1693
5924
4924
9900
3547

1612
6283

1170
4329
532
389
Mg

two mixtures of the three components: one by simple mixing and

another by intimate mixing, and then pyrolyzed them in an
entrained flow reactor at 950  C. It was found that the yield of CO2
increased with the intimacy of the mixture. Therefore, the effect of
331.2

379.6
1800

3310

1400
1092

1020
125

170

187
115
837

518
746

533
205

614
132
9.0
24

interactions between components may differ in a physical mixture

Fe

from an actual biomass sample as the structure of biomass will

affect the outcome of pyrolysis, altering the selectivity towards
certain products [144].
15710
188.4

209.0
1653

1911

3642

2455
140

148

100
Inorganic content in representative biomass feedstock [82,100,101,111,123].

The conditions for pyrolysis process, viz. temperature, heating

4.6
10

73
Al

e
e
e

rate, residence time, pressure, environment, catalyst, etc. pro-

foundly determine the nature of products [145]. Henceforth
depending on the desired product type, pyrolysis conditions can be
3387.8

8507.3
25000
30000
82560

12970

867.2
1518

1501
3126

4686
3737
1900

6255
1793
4772

6025
7666

adjusted. It is well-understood from literature that high tempera-

477

182
Ca

tures and short residence times favor the formation of condensable

products, while high temperatures and longer residence times
Inorganic content, ppm

favor the formation of non-condensable gaseous products, because

2703.2

3879.8
28000
28000
19470

26283

30500
17690

28930
380.5

of the occurrence of secondary reactions. Solid products are usually

2682

2438
1965

9366

7094

3860
9061
5402

614
32

favored at low temperatures [146]. Depending on the process

K

conditions the pyrolysis process can be classified into following

ppm inorganic in ash of biomass.

categories:
10564
2000

4140
1758
1243

6463
1298

1427

5106

7861
22.9

32.1

25.9
141

467

132

ppm inorganic in biomass.

Na

93

80

10

92

5.1. Fast pyrolysis

Fast pyrolysis is an advanced technology that has been gaining

attention because of the increasing interest in the production of
Groundnut shella
Elephant grassa
Cattle manurea

Coconut shella

liquid fuel from biomass. It is a continuous process. The purpose of

Wheat strawa
Coconut coira
Beech wooda
Birch wooda

Millet huska
Corn stalksa

Rice strawa
Feed stock

fast pyrolysis is to prevent further cracking of the pyrolysis prod-

Rice huska
Corn coba
Coir pitha

Subabula
Bagassea
Albiziab

Spruceb
Cottona

ucts into non-condensable compounds. In fast pyrolysis, the pro-

Irokob
Table 2

cess parameters are carefully controlled to give high oil yields. The
a
b

primary requirement of fast pyrolysis is high heat transfer rates,

702 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716
which can be achieved by finely grounding the feed biomass. The
feed is heated at high temperatures (450e600  C) for short resi-
dence times (typically less than 2 s). Liquid yield as high as 75% on
dry feed basis has been reported for fast pyrolysis of wood
[147,148]. Since, the reaction takes place for a very short duration,
not only chemical kinetics, but also rate of heat and mass transfer,
and transition phenomena play a crucial role in determining the
product chemistry. Desirable products can be produced by setting
process parameters at optimum [147].
5.2. Intermediate pyrolysis
Intermediate pyrolysis is carried out in the temperature range of
300e500  C. Compared to fast pyrolysis, the liquid products ob-
tained from intermediate pyrolysis have low tar yield and viscosity.
More controlled chemical reactions take place, and thus the reac-
tion conditions in intermediate pyrolysis offer a broad range of
variation for process optimization. Although lower liquid yields (up
to 55%) are obtained in this operation, large biomass sizes (coarse,
shredded, chopped or ground) are acceptable [147].
An intermediate pyrolysis reactor (Pyroformer), operating in the
temperature range of 400e500  C, has been developed by Euro-
pean Bioenergy Research Institute (EBRI) at Aston University. The
unit is driven by the thermal energy obtained from the char pro-
duced [149].
5.3. Slow pyrolysis
Slow pyrolysis is a batch process which is carried out at low
temperatures and slow heating rates, for long residence times. This
process is more tolerant to the moisture content in the feedstock.
Although most literature present in slow pyrolysis is based on its
use for production of solid fuel, liquid fuels can also be produced
from this operation [150]. Carbonization is the slow pyrolysis of
biomass without condensing the pyrolysis products. It is the oldest
technique of treatment of biomass for the production of charcoal;
and is carried out where biochar is the desired product. The vapors
are usually not condensed in this operation but can be used for
providing the heat for operation, by direct or indirect heating.
Heating rates as low as 0.1e2  C, have been reported [151]. Mois-
ture affects the char properties, which are helpful in producing
activated carbons through pyrolysis. Moisture content of 15e20% is
typical for charcoal making [152,153]. The feed size can vary from
briquette size to whole logs. Although, wood is the predominant
feedstock for slow pyrolysis, other feedstock such as cashew nut
shells and palm have also been reported [154,155].
Torrefaction is another slow pyrolysis operation, which is con-
ducted in the temperature range of 225e300  C. It is a mild
Fig. 2. Thermal analysis of biomass components: (a) TGA, (b) DSC.
pyrolysis process that aims at increases the energy density and fuel
properties of biomass [156]. During torrefaction process, the water
contained in the biomass, as well as superfluous volatiles, are
removed, while the biopolymers (cellulose, hemicelluloses, and
lignin) partly decompose by giving off organic volatiles [118]. The
end product is the residual solid, dry, blackened material which is
termed as “torrefied biomass” or “bio-coal”. The product is free
from volatiles and has much higher energy density than the parent
biomass. The decrease in weight and volume of the biomass also
enables its easy transportation over long distances to plants for use
or further processing. Torrefied biomass is also hydrophobic,
meaning it can be stored for long time durations without absorbing
water. Torrefied biomass also requires less energy to crush, grind, or
pulverize; and the same tools as for crushing coal can be used
[118,157].
5.4. Hydropyrolysis
Other than the inert nitrogen environment for pyrolysis, py-
rolysis in reductive hydrogen environment has also been studied by
several researchers. In hydropyrolysis, as the reaction takes place
under the pressures of hydrogen, the formation of free radicals is
hindered. The amount of unsaturated hydrocarbons reduces
thereby increasing the quality of the bio-oil formed. The probable
reaction mechanism under nitrogen environment could be the
random thermal cracking of the large biomass molecule which
leads to an increased variation in the products formed. However, in
the presence of hydrogen, it could be the systematic bond cleavage
(initiation with hydrogenolysis/hydrogenation, bond breaking in
the order of increasing bond strength and stability of formed
components) in the macromolecular structure which leads to the
formation of few products with higher selectivity [34,158].
Putun et al. [69] reported a 40% increase in the bio-oil yield
when pyrolysis of sunflower bagasse was conducted under
hydrogen pressure (150 bar). Balagurumurthy et al. [159] studied
the pyrolysis of rice straw under hydrogen and nitrogen environ-
ments and showed that the reaction mechanism is different in both
cases as the product portfolio was different in the two atmospheres.
The bio-oils obtained under hydrogen atmosphere showed more
selectivity towards phenolic compounds. Although the higher yield
of bio-oil was obtained under the nitrogen atmosphere, the selec-
tivity towards phenolic compounds was less [159].
An integrated gasification-hydropyrolysis process has been
developed and patented by Agarwal and Singh [160]. This low-cost,
process has been demonstrated for the production of high liquid
yields using H2 as well as the heat required for the biomass fast
pyrolysis supplied by the syngas derived from gasification or
reforming of Carbon-Containing Moiety (CMM).
 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716
6. Reactor configurations
A further level of complexity to the pyrolysis operation is added
by the type of contact between particles in the reactor and depend
on the configuration of the pyrolysis reactor [103]. Some of the
traditional reactor configurations that have been used for pyrolysis
are as follows.
6.1. Fluidized bed reactors
Fluidized bed reactors (FBR) are the most researched and one of
the most successful pyrolysis reactors [30]. In these reactors, rapid
heating of biomass particles takes place by mixing them in a stream
of moving sand particles at high temperatures. The volatile mixing
of sand with biomass particles leads to high heat and mass transfer
coefficients, a favorable condition for fast pyrolysis. The bed is
heated by externally combusting the bio-oil/char produced, and
transferring this heat to the bed directly (adding hot solids to the
bed) or indirectly (hot gas/steam passed through the tubes in the
bed). FBR also has a simpler design, easy scale-up, and proficient
control over the residence time. However, large reactor size, and
the high cost of construction and operation are the disadvantages
[20].
The FBR are mainly classified into three basic types: (a)
bubbling, (b) entrained, and (c) circulating. The fundamental theme
in these reactors is that the biomass suspension sanctions a rapid
thermochemical conversion. In the bubbling fluidized bed reactors
(BFBR) (Fig. 3), the gas velocity is usually in the range of 1.5e2 times
the minimum fluidization velocity. The entrained fluidized bed
reactor (EFBR) operates at co-current flow, where the biomass
particles fall freely under gravity or entrained under the influence
of gas drag force [147].
Fundamental studies on the FBR were carried out at the Uni-
versity of Waterloo, Canada, in the 1980s. Later, the corporate
commercialization of the FBR technology of the University was
done by the Canadian company, Dynamotive Corporation. In 2002,
Dynamotive Corporation commissioned a commercial plant in
West Lorne, with a capacity of 100 tons of sawdust per day. Another
plant of capacity 200 tons/day was built in Guelph in 2006 [8]. In
1990, a pilot FBR of capacity 200 kg/hr, was built at Union Fenosa,
Spain [161].
The innovation of circulating fluidized bed reactors (CFBR)
(Fig. 4) took place in 1978 when Choi et al. [162] was awarded a
patent for developing a loop pyrolysis process for organic waste
solids. In CFBR the gas velocity is considerably higher than BFBR
and EFBR, to permit entrainment and circulation of the bed mate-
rial between a riser, where customarily the reaction takes place,
and a downer, where solids are re-circulated back to the riser part
of the system. CFBR are more complicated than the other FBR
configurations. Compared to BFBR the residence time of the char is
practically the same as the residence time of the gases and vapors.
Due to greater gas velocity, the char is transported quickly through
Fig. 3. Bubbling fluidized bed reactor.
703
the reactor, which usually leads to higher char content in the py-
rolysis oil. A countermeasure is to employ a filter to screen off the
char particles. High throughput is the main advantage of CFBR. The
heat for the process is gathered by burning the char for heating the
sand in a separate reactor unit, and recirculation of the hot sand
into the reactor [163].
6.2. Ablative reactors
The mechanism of pyrolysis in the ablative reactors (Fig. 5) is
similar to melting of butter on the surface of a frying pan. In these
reactors, the thermal “erosion” of the biomass takes place by
pressing against the hot reactor wall. The rate of reaction is strongly
influenced by pressure, the relative velocity of the biomass on the
heating surface, and the reactor surface temperature. This type of
reactor accepts a feedstock of large sizes and allows good me-
chanical abrasion of char. In the 1980s, fundamental work on
ablative pyrolysis reactors was done at CNRS in Nancy, France
where research was carried out on the relationship between
pressure, motion, and temperature [164]. Later, NREL (formerly
known as SERI) in Boulder, Colorado developed an ablative vortex
reactor, in which the biomass was accelerated to supersonic ve-
locities to derive high tangential pressures inside a heated cylinder.
However, the problem of insufficient biomass conversion, requiring
recycling was observed in this work [165]. In the 1990s, Peacocke
and Bridgewater [162] (Aston University), successfully built and
operated a prototype rotating blade ablative reactor of capacity
3 kg/hr, with the liquid yield of 80%. In the continued work on
ablative cyclone reactors at CNRS, France, bio-oil yield up to 74% has
been reported [166]. In Germany, ablative reactors of capacity
250 kg/hr have been commissioned by Fraunhofer UMSICHT and
PYTEC, at Sulzbach-Rosenberg and Hamburg respectively. PYTEC
also plans for the demonstration of a pilot plant of capacity 2 ton/hr
in Mecklenburg-Vorpommern [167,168].
Some disadvantages of ablative reactors are [147]:
Fig. 4. Circulating fluidized bed reactor.
Fig. 5. Ablative pyrolysis reactor.
704 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716
(a) The problem of heat transfer from the hot surface of the
reactor, because of low heat transfer coefficient and indirect
heating employed.
(b) Since the feed is to be eroded against the reactor wall, par-
ticle morphology, size, and free-flowing characteristics pose
significant restriction.
6.3. Rotating cone
The major research in the development of rotating cone reactors
(Fig. 6) has been done at Twente University of Technology, and
Biomass Technology Group (BTG) [169,170]. In rotating cone re-
actors the biomass is fed near the bottom of the rotating cone and is
carried up the wall of the rotating cone in a spiral motion due to the
centrifugal force. Flash heating of the biomass can be achieved with
high heat transfer by the wall and heated sand. The foremost
advantage of this configuration is that no carrier gas is needed to
transport the vapors, which reduces the operating cost.
A pilot plant based on the rotating cone reactor having a ca-
pacity of 2 tons per hour, has been installed by BTG in Malaysia. The
plant gets its feedstock, empty fruit bunches from a closely located
palm mill [171].
6.4. Auger/screw reactor
Auger (or screw) reactors (Fig. 7) are tubular, continuous re-
actors in which solid biomass is transported via a rotating screw,
while the heat required for pyrolysis is transported along the
tubular wall of the reactor. The screw thereby fulfills two purposes:
first, it mixes the feed and second, it controls the residence time of
the biomass in the reactor. An essential advantage of this reactor
configuration is that it can be built very compact and in some cases
even portable; this allows the reactor to be used on the site of
biomass generation or where the biomass is abundantly available.
On-site conversion of biomass reduces the cost of operation, by
saving the cost of transport of feedstock to biorefinery [172]. Ingram
et al. [173] conducted fast pyrolysis of wood biomass in an auger
reactor. It was observed that bio-oil produced in their work was
comparable to the bio-oils produced by fast pyrolysis in fluidized
bed and vacuum pyrolysis processes. However, lower heat transfer
rates were observed in the process, in comparison with those
Fig. 6. Rotating cone pyrolysis reactor.
Fig. 7. Auger/Screw pyrolysis reactor.
achieved in fluidized bed reactors, suggesting noteworthy possi-
bility of further improvements.
A modular and transportable bio-oil plant based on auger
reactor has been demonstrated by Renewable Oil International, LLC
(ROI), Florence, AL [172]. Another mobile pyrolysis technology
(Pyroformer™), based on intermediate pyrolysis in auger reactor
has been developed by EBRI at Aston University. The pyrolysis va-
pors produced from Pyroformer™ are quenched using diesel as the
quenching medium which is recirculated in a closed loop until the
required blend of pyrolysis liquid in diesel is reached. The mobile
unit has been successfully demonstrated for providing continuous
power to a school in Khusapura village in India [174]. Some of the
popular pyrolysis units installed worldwide are tabulated in
Table 3.
7. Bio-oil from pyrolysis
Bio-oil is the term given to the dark brown, freely-flowing liquid
obtained from pyrolysis of biomass. This liquid is not the product of
thermodynamic equilibrium but is produced by rapid cooling or
quenching of the gaseous products. The liquid also comprises of
some fragments of cellulose, hemicellulose, and lignin, which were
able to cross the pyrolysis environment by volatilization or by being
part of a liquid droplet small enough to be entrained from the
reactor [176].
Due to the moist raw material, and water produced as a
consequence of the secondary reactions during storage of bio-oil,
the liquid product of biomass pyrolysis many represents two
distinct phases (aqueous phase and organic phase). The organic
phase can be used as fuels directly or upgraded to high-grade fuels
or chemical material. Whereas the aqueous phase consisting of a
large amount of water soluble of compounds such as acetic acid,
hydroxyl acetone, and phenol, cannot be used as fuels directly
[177]. A catalytic reforming process for the production of hydrogen
via catalytic upgradation of the aqueous phase has been reported in
the work of Li et al. [178].
7.1. Physiochemical properties
The physiochemical properties of the bio-oils obtained from
pyrolysis, vary significantly from those of conventional mineral oils.
The oil properties and composition are dependent on several fac-
tors such as feed biomass, moisture content in the feed, process
parameters (vapor phase residence time, temperature, and pres-
sure), reactor type, recovery design unit and the scale of operation
[162]. Bio-oils contain extensive moisture content, suspended
solids, char, oxygen and acidic compounds. These constituents have
 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716 705

Table 3
Pyrolysis units worldwide [20,175].

Country Organization Technology Capacity (kg/hr) Status

Canada ABRITech/Advanced Biorefinery Inc., Forespect Auger 70e700 Operational

2000 Commissioning
Canada Agri-Them/University of Western Ontario Fluid bed 420 Upgrade
Canada & USA Ensyn several Circulating fluidized bed 3e3100 Operational
Chile UDT Fluid bed 15 Operational
China University of Science & Technology of China, Hefei Fluidized bed 120 Operational
Finland Fortum Fluid bed 10000 Construction
Finland VTT Fluidized bed 20 Operational
Finland Metso Fluidized bed 300 Operational
Germany Fraunhofer UMSICHT Ablative 250 Commissioning
Germany KIT Twin auger 200 Operational
Germany Pytec Ablative 250 Commissioning
Malaysia Genting Rotating cone 2000 Dormant
Netherlands BTG BioLiquids EMPYRO Rotating 6500 In design phase
South Korea Korea University of Science and Technology Tilted slide reactor 12.5 Operational
UK Biomass Engineering Ltd. Fluidized bed 420 Upgrade
USA GTI Hydropyrolysis 50 e
USA Iowa State University Fluidized bed 10 Operational
USA Mississippi State University Auger 200 Construction
USA National Renewable Energy Laboratory Fluidized bed 12 Operational
USA Red Arrow/Ensyn several Circulating fluidized bed 128e1250 Operational
USA Renewable Oil International LLC Auger/moving bed 105 Operational
USA RTI International Catalytic fast pyrolysis 40 Construction
USA UOP Circulating fluidized bed 40 Construction
USA Virginia Tech Fluidized bed 250 Operational

Table 4 7.1.2. Oxygen content

Physical properties of bio-oil from pyrolysis, and mineral oils [175,179]. The presence of oxygen is one of the major differences between
Property Typical Bio-oil Heavy Fuel Oil Light Fuel Oil the bio-oils and the hydrocarbon fuel, leading to low energy density
Water, % 20e30 ~0 ~0
(less than 50%) and immiscibility with conventional fuels. Oxygen
Suspended solids, % Below 0.5 e e content up to 35e40% distributed over 300 compounds has been
Ash, % 0.01e0.1 0.08 (max) 0.01 (max) reported in the literature [183]. The majority of these compounds
Nitrogen, % <0.4 0.4 0.02 fall into the category of carboxylic acids, hydroxyaldehydes,
Sulphur, % <0.005 1.0 (max) 0.001 (max)
hydroxyketones, sugars and phenolics [184]. Some of the common
Viscosity (40  C), cSt 15e35 180e420 2.0e4.5
Density (15  C), kg/dm3 1.10e1.30 0.99e0.995 0.845 (max) oxygenated hydrocarbons found in bio-oil are given in Fig. 8.
Flash point,  C 40e110 65 (min) 60 (min)
Pour point,  C 9 to 36 15 (max) 5 (min)
7.1.3. Viscosity
LHV, MJ/kg 13e18 40.6 42.6
pH 2e3 e e The viscosity of the bio-oil can vary from 35 to 1000 cP (at
40  C), depending strongly on the nature of feedstock, processing,
and pre-processing conditions, and also on the efficiency of
collection of low boiling components [183]. The viscosity of bio-oil
low heating/calorific values. While mineral oils have oxygen con-
tends to increase with storage time, as a result of chemical reactions
tent at ppm level, bio-oils comprise of 35e40% oxygen, present in
taking place in-between the bio-oil constituents [182].
several organic functional groups. These functional groups are also
responsible for highly polar nature of the bio-oil [175]. Different
physiochemical properties of bio-oil obtained from pyrolysis of 7.1.4. Acidity
biomass are tabulated in Table 4 and summarized as follows. The carboxylic acids, such as acetic acid and formic acid present
in the bio-oil, increase its acidity (pH 2e3) and make it corrosive for
the handling equipment and storage vessels, essentially at high
temperatures and high water content.
7.1.1. Moisture content
Water is attached to the lignin oligomers present in the biomass, 7.1.5. Ash
because of the presence of polar hydrophilic functional groups. Ash derived from the parent feedstock is present in the bio-oil at
Moisture in the bio-oil is present as the single most abundant variable concentrations. It is mainly composed of the alkali metals
compound. Depending on the source of feedstock, bio-oil can have such as sodium, potassium, and vanadium. Sipila € et al. [22] ob-
15e30% moisture content [119,180]. Some moisture is also acquired tained ash content in the range of 0.09e0.14% in the pyrolysis oils
as the product of dehydration reactions taking place during py- derived from different wood biomass.
rolysis. Bio-oil moisture as high as 40e60% has been reported in the
work of Su et al. [181], who conducted pyrolysis of furniture 7.2. Typical composition
sawdust, comprising of 9.1% moisture in the feed.
Czernik et al. [182] observed an increase in moisture content of The organic constituents of a typical bio-oil can be categorized
the bio-oil produced from the pyrolysis of wood biomass, with in the families such as acids, alcohols, aromatics, esters, furans,
storage time, and attributed it to the occurrence of etherification ketone, phenols, sugars, etc. [180]. Oligomeric fractions of lignin are
and esterification reactions taking place in-between the bio-oil also significantly present in the bio-oil. The molecular weight of
components. these oligomers can be as high as 5000 [12,185].
706 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716

Fig. 8. Typical oxygenated hydrocarbons found in bio-oil.

Table 5
Typical composition of bio-oil obtained from different feedstock.

Feedstock Major constituents of bio-oil (in order of decreasing abundance) Ref.

Albizia Nonaromatic aldehydes, acids, nonaromatic ketones, furans, sugars [100]

Babool seeds Hydrocarbons, alcohols, phenols [53]
Beech Nonaromatic aldehydes, nonaromatic ketones, acids, sugars, furans, pyrans [100]
Cedrus deodara Phenols, aromatic ethers, acids, hydrocarbons, carbonyl compounds, alcohols [34]
Corn cob Nonaromatic ketones, acids, nonaromatic aldehydes, sugars, furans, lignin-derived phenols [100]
Cotton residue Phenols, aromatic ethers, hydrocarbons, ketones, carbonyl compounds [186]
Iroko Nonaromatic aldehydes, nonaromatic ketones, acids, furans, sugars [100]
Oil Palm Empty Fruit Bunches Phenol, furan, ketone, alcohol, acids, pyrans [187]
Oil palm shell Phenols, acids, ketones, alcohols, furans [188]
Palm frond Acids, phenols, ketones, aldehydes, alcohols [189]
Pinewood Acids, phenols [190]
Rice husk Acids, aromatic, heterocyclic compounds [191]
Rice straw Acids, esters, phenols, alcohols, ketones, furans [180]
Scenedesmus dimorphus Aromatics, phenols, heterocyclic hydrocarbons, amides, indole [78]
Scenedesmus sp. Fatty oxygenates, N-containing compounds, aromatics, carbohydrate pyrolysates, alkanes, alkenes [77]
Spruce Nonaromatic aldehydes, sugars, nonaromatic ketones, guaiacols, acids, furans, pyrans [100]
Wild Reed Phenols, acids, ketones, aromatics, aldehydes, alcohols [119]

Table 5 presents the major constituents of bio-oil as reported in
the literature for different biomass.
7.3. Bio-oil analysis
Characterization of bio-oil is an attempt to find the composition
through various analytical techniques. Gas chromatography-mass
spectrometry (GC/MS) is the most commonly used characteriza-
tion method reported in the literature for analysis of the organic
fraction of the bio-oil. The GC section of the equipment separates
the individual components of the bio-oil mixture via volatilization
of the mixture through GC column, followed by identification of
these components at MS. The popularly used GC columns for
analysis of bio-oil as reported in the literature are, BP5 (5% Phenyl/
95% Dimethyl Polysiloxane) [192], DB-5ms (Phenyl Arylene poly-
mer) [5,78], and HP-5 ((5%-Phenyl)-methylpolysiloxane) [87]. For
analysis of the aqueous fraction use of high-pressure liquid chro-
matography (HPLC) has been reported [193]. Other common
methods reported in the literature for analysis of bio-oil include
Proton nuclear magnetic resonance (1H NMR) and Fourier trans-
form infrared spectroscopy (FT-IR).
Pyroprobe gas chromatography-mass spectrometer (Py-GC/MS)
is a state of art characterization technique for effective research in
the field of biomass pyrolysis. It enables an online analysis of the
products of pyrolysiss reaction taking place in the pyroprobe and
thus identifying all evolved species over a particular temperature
range [64,100,194,195].
A better comparison of bio-oils with diesel fuel can be made by
comparing the elemental composition, and HHV of the two fuels. O/
C ratio of bio-oils is much higher than the conventional diesel fuels,
subsequently decreasing its heating value. Low N/C and S/C ratios
are desired in fuel for better emission control. Table 6 presents a
literature survey of elemental analysis of different bio-oils, in
comparison with standard diesel fuel.
 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716 707

Table 6
Elemental analysis of bio-oil.

Feed stock Moisture,% C, % H, % N, % S, % O, % Ash, % HHV, MJ/kg Ref.

Diesel e 81.38 11.86 0.1013 0.126 6.53 e 46.25 [196]

Albizia 25.1 41.9 7.4 0.6 0.00 50.1 0.2 17.4 [100]
Babul 26.36 50.92 8.27 2.23 e 38.57 0.03 22.21 [197]
Banana leaves e 55.9 7.8 0.87 0.08 35.3 e 25.0 [58]
Beech 22.0 41.4 7.1 0.2 0.10 51.2 0.2 16.9 [100]
Birch 18.9 44.0 6.9 <0.1 0.00 49.0 0.004 16.5 [198]
Cashewnut 3 79.9 11.8 <0.2 e 8.1 0.01 40 [107]
Corn cob 32.2 38.1 8.0 0.7 0.00 53.2 0.1 15.8 [100]
Esparto grass e 75.82 11.76 0.26 e 12.15 e 34.8 [117]
Garlic stem 57.06 14.42 9.26 1.37 0 74.95 0 7.25 [62]
Iroko 32.3 38.2 7.5 0.3 0.00 54.0 0.2 15.9 [100]
Jute stick e 47.18 8.36 e e 44.13 0.33 21.09 [85]
Microalgae S. dimorphus e 74.73 10.60 5.79 0.61 8.27 e 28.52 [78]
Oak 16.3 46.9 1.5 0.0 e 52.7 0.09 e [199]
Oil Palm Empty Fruit Bunches 18.74 49.80 7.98 1.93 e 40.29 0.65 21.41 [187]
Pepper stem 52.03 15.53 7.18 0.33 0 76.30 0 5.01 [62]
Pine 17.0 45.7 7.0 <0.1 0.02 47.0 0.03 17.2 [198]
Poplar 18.9 46.5 7.2 0.15 0.02 46.1 0.01 17.4 [198]
Rape plant e 57.29 6.63 1.03 0.20 34.84 0.01 27.15 [52]
Rapeseed cake 0.001 73.74 10.69 4.65 0.11 10.51 0.30 36.4 [200]
Southern pine 10.2 46.0 7.9 0.1 e 46.0 0.03 e [199]
Spruce 22.0 42.3 7.2 0.2 0.00 50.3 0.1 17.2 [100]
Sugarcane bagasse e 46.27 6.55 0.0 e 46.94 0.24 20.07 [85]
Swine manure 43.85 43.88 8.57 3.85 0.35 43.35 0.48 13.59 [122]
Switchgrass 16.7 38.8 8.5 0.0 e 45.6 1.04 e [199]
Waste paper e 40.80 6.29 0.0 e 52.91 0.35 13.10 [85]
Wild reed 33.43 31.79 8.31 1.08 0 58.82 0.0001 15.17 [119]
Wood 15e30 54e58 5.5e7.0 0e0.2 e 13.19 0e0.2 16e19 [201]

7.4. Upgradation of bio-oil 7.4.2. Hydrodeoxygenation

Upgradation of pyrolysis vapors by various means, physical,
chemical, catalytic, etc., has been researched by several research
groups to improve bio-oil properties, and enable its usage as ‘fuel’.
Upgrading is desirable to reduce the oxygen content in the oil and
make it resemble crude oil.
7.4.1. Physical upgradation
Hot vapor filtration is the most common method of physical
upgradation of bio-oil, by removal of ash from the organic vapors
before condensation. It can provide considerable ash reduction
compared to conventional cyclone separation. Decrease in the
content of alkali metals up to 10 ppm has been reported [202].
Major work in hot vapor filtration has been carried out at NREL
[203], VTT and Aston University [204].
Agblevor and Bessler [75], used hot vapor filtration on the va-
pors produced in pyrolysis of switchgrass. It was observed that
although the yield of condensable didn't change, the bio-oil pro-
duced was not as dark as the oils from the cyclone separator, sug-
gesting a decrease in the level of suspended char in the oil.
Another method of physical upgradation is the addition of low
molecular weight solvents to the bio-oil. Solvents such as ethanol
and methanol can considerably alter the viscosity and storage
stability of the oils. The addition of these solvents shifts the stoi-
chiometry from polymers to oligomers which are stabilized by the
solvent groups [204]. Diebold [205] reported a 20 times decrease in
the rate of aging, by the addition of 10% methanol in the bio-oil.
Although bio-oil is immiscible in diesel, an emulsion of the two
can be prepared using suitable emulsifying agents, in order to
improve the fuel characteristics of the bio-oil. Ji-lu [191] studied the
emulsions of bio-oil obtained from pyrolysis of rice husk in diesel,
in terms of LHV and acidity. As the bio-oil to diesel ratio was
increased from ~1:3 to ~3:1, LHV decreased from 34.55 to 23.65 MJ/
kg, while pH shifted from 2.7 to 2.2.
In hydrodeoxygenation (HDO), oxygen is removed from
oxygenated hydrocarbons by reaction with hydrogen at high
pressures in the presence of a catalyst. Major studies conducted on
HDO, are based on model compounds found in bio-oil. Zhang et al.
[206] studied HDO of pyrolysis oils using cobalt molybdate catalyst
and reported a reaction order of 2.3 for the reactions taking place.
Using the similar catalyst, Furimsky [207,208] studied the HDO of
furan and tetrahydrofuran and stated the mechanisms and kinetics.
Gevert et al. [209] investigated the HDO kinetics of a series of
mono- and dimethyl substituted phenols over sulfide cobalt
molybdate catalyst. Non-sulfided catalysts, such as Pt/SiO2/Al2O3
[210], vanadium nitride [211], and Ru [212], have also been used for
HDO. A comprehensive review on the chemistry of HDO process has
been published by Furimsky [213].
7.4.3. Catalytic cracking of pyrolysis vapors
Catalysts can be used to improve the quality of the pyrolysis
products, by two routes. One is catalytic upgradation of the bio-oil
as the downstream process, using metallic or bifunctional (hydro-
genating and acidic) catalysts [214,215]. The other route comprises
of in-situ upgradation by integrated catalytic pyrolysis, in which the
catalyst is added into the pyrolysis system.
The vapors produced in the pyrolysis reaction undergo further
cracking inside the pores of the catalyst to form low molecular
weight compounds. Although the yield of condensable organic
compounds tends to decrease in this system, there is a significant
increase in the product quality in terms of low oxygen content and
enhanced calorific value. Product selectivity is also an attractive
feature of catalytic pyrolysis, the selectivity being dependent on
catalyst pore size and nature of active sites [216]. Several catalysts
such as AlMCM-41 [217], HY [195], HZSM-5 [218], silicalite [216], Y-
Zeolite [216], ZSM-5 [219], have been researched for integrated
catalytic pyrolysis. Use of metal doped ZSM-5 catalysts (ZnZSM-5
[220], MnZSM-5 [221] and GaZSM-5 [222]) has also been reported
in the literature.
708 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716

In the experiments conducted by Zhang et al. [195] on pyrolysis CO/H2 ratio at a given temperature [229,230].
of Aspen lignin, the oxygen content in the product hydrocarbon Hydrogen production from steam reforming of bio-oils in fixed
dropped from 28% to 4%, consequently increasing the HHV to bed and fluidized bed, along with the reaction mechanisms of the
46 MJ/kg, when HZSM-5 was used to catalyze the reaction. The use model compounds has been extensively studied by NREL [231,232].
of HZSM-5 also increased the yield of toluene. Most of the work Hydrogen is a clean energy resource and crucial in the chemical
reported in the catalytic pyrolysis has been done with solid acid industry. The increasing focus on reforming the water fraction of
catalysts. However the use of basic oxides ZnO [223] and MgO [224] bio-oil looks promising.
has also been reported. These catalysts show higher selectivity
towards aldol condensation and transesterification reactions [2].
7.5. Applications of bio-oil
Carlson et al. [216] mentioned undesirable coke formation as a
major challenge in catalytic pyrolysis and emphasized on the
The bio-oil obtained from pyrolysis can be used for heating,
reduction of coke formation by applying fast heating rates, main-
without altering the machine designs considerably. Kurji et al. [233]
taining high catalyst to feed ratios, and making apt catalyst
tested the blends of bio-oil obtained with pyrolysis for running
selection.
turbines. The use of bio-oil for heating in furnaces, kilns, and boilers
Zhang et al. [225] investigated the fast pyrolysis of corncob with
has also been demonstrated [150].
and without catalyst (HZSM-5) in a fluidized bed reactor to deter-
Stamatov et al. [150] studied combustion characteristics of bio-
mine the effects of pyrolysis parameters on the product yield and
oils produced from slow pyrolysis of several Australian eucalyptus
the quality of the liquid products. Use of HZSM-5 reduced the O/C
species in a jet spray. Compared to diesel fuel, the flames of bio-oil
ratio of the produced bio-oil from 0.582 to 0.149, leading to a sig-
at same combustion conditions were reported as shorter, wider and
nificant increase in HHV of the product from 18.8 to 34.6 MJ/kg.
brighter. Adding of flammable polar additives (e.g. ethanol) to bio-
Almost ten times increase in aliphatic hydrocarbons was observed
oil improved some of the undesired properties of the fuel such as
in liquid yield, along with a decrease in acidity from pH 2.8 to 5.2.
poor atomization, low calorific value, and high NOx emission from
Adjaye and Bakhshi [226], studied the upgradation of pyrolysis
the flame. It was also concluded that since ethanol addition leads to
oil from maple wood using HZSM-5, HY, H-mordenite, silicalite, and
the reduction of heat flux from the flame, its addition in bio-oil can
silica-alumina catalysts. Hydrocarbon content as high as 89% was
be an optimizing factor in achieving the proper balance between
obtained in the organic distillate fraction obtained from the
the best spray formation and the maximal heat flux from the flame.
upgradation process. Moreover, HZSM-5 and H-mordenite showed
Fig. 9 shows different routes for utilization of bio-oil. The ap-
more selectivity towards aromatic hydrocarbons within the gaso-
plications of bio-oil are not limited to fuel blends. Hundreds of the
line boiling range.
components of bio-oil have been determined, which arouse great
Horne and Williams [227] studied pyrolysis of pine wood fol-
interests among researchers. Many industrially important chem-
lowed by upgradation of products over ZSM-5 catalyst. It was
icals can be extracted from bio-oil, such as phenols used in the
observed that on using catalyst, the oxygen content in the bio-oil
resins industry, volatile organic acids used for the formation of de-
reduced from 33 to 13%.
icers, levoglucosan, hydroxyacetaldehydes and some additives
Horne et al. [226] studied catalytic upgradation of pyrolysis oil
applied in the pharmaceutical, fiber synthesizing or fertilizing in-
obtained from the pyrolysis of waste wood, using a ZSM-5 catalyst.
dustry and flavoring agents in food products [1,38]. Hydrox-
The presence of catalyst increased the yield of aromatic hydrocar-
yaldehydes can be present in bio-oils in concentrations as high as
bons, by a factor of 86. When pyrolysis vapors were processed with
17%. High concentration of this aldehyde has been reported in the
methanol as an additive, a considerable increase in alkylated
bio-oil obtained from the pyrolysis of wood-based biomass [21].
phenolic and aromatic hydrocarbons was observed.
They are used as the browning agent for cheese, fish, meat, poultry
Catalytic upgrading the volatiles before their condensation is
and sausages. A range of food flavoring products, based upon bio-
currently considered as the most promising method to minimize
oil, has been patented and commercialized by Red Arrow Prod-
the negative characteristics of bio-oil. During the catalytic
ucts Company (USA) and by Chemviron (Germany) [8]. Commer-
upgrading process, the moisture and oxygen contents of bio-oil are
cialization of these special chemicals from bio-oils requires more
minimized, the molecular weight is reduced, and some bio-oil mass
devotion to developing reliable low-cost separation and refining
is reduced in favor of char and gaseous species. The ideal catalyst
techniques.
should be highly active, selective to particular products, resistant to
The phenolic compounds present in the bio-oil such as meth-
deactivation, readily recycled and cheap [228].
ylphenols (cresols), methoxyphenols (guaiacol),
7.4.4. Steam reforming
Steam reforming is the process of converting hydrocarbons into
syngas (CO þ H2), by reaction with steam at high temperatures. The
oxygenated hydrocarbons obtained from the pyrolysis of biomass
can be steam reformed by following empirical reaction:

CxHyOz þ (x e z)H2O /xCO þ (x e z þ y/2)H2 (5)

CxHyOz þ (2x e z)H2O /xCO2 þ (2x e z þ y/2)H2 (6)

Equation (1) is the primary steam reforming reaction; however,

it is also accompanied by water gas shift reaction, giving the overall
empirical reaction as:
Being an endothermic reaction, steam reforming is favored at
high temperatures. Low pressures also favor the reforming reac-
tion, as per Le Cha^teliers principle. High temperatures increase the
CO/H2 ratio while increasing the steam to carbon ratio lower the Fig. 9. Applications of pyrolysis products (modified from Ref. [146]).
 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716 709

methoxypropenylphenol (isoeugenol), etc., have a significant eco-
nomic potential, in food, pharmaceutical and paint industries
[234,235]. Patel et al. [236] demonstrated a method of selective
extraction of phenols from the bio-oil produced from sugarcane
bagasse pyrolysis by supercritical fluid extraction (SCFE) route. The
phenols and substituted phenols obtained after extraction can be
used as natural phenols for preparing phenol-formaldehyde resins,
this reducing the dependence on petro-based phenols for resin
manufacturing.
Pavlath and Gregorski [237] pyrolyzed five carbohydrate prod-
ucts (amylase, cellobiose, cellulose, glucose, and maltose) and
showed that furfural and furfuryl alcohol up to 30% and 12e30%
respectively were produced. Furfuryl alcohol is a useful chemical
intermediate in the manufacture of furan resin prepolymers, which
are exploited in thermoset polymer matrix composites, cement,
adhesives, casting resins and coatings. Furfuryl alcohol is also used
for the production of tetrahydrofurfuryl alcohol which is used as a
nonhazardous solvent in agricultural formulations and as an
adjuvant to help herbicides penetrate the leaf structure. Furfural is
an important chemical solvent which can be used to make other
furan chemicals, such as furoic acid, via oxidation, and furan itself
via palladium catalyzed vapor-phase decarbonylation [238].
The aqueous phase of the bio-oil comprised of modest con-
centrations (~3%) of calcium carboxylates including calcium acetate
and calcium formate. These salts have potential applications in
deicing, sulfur dioxide removal during fossil fuel combustion, and
as a catalyst during coal combustion [239].
8. Biochar
Biochar, charcoal or char, is the solid carbon-rich residue left
after pyrolysis of carbonaceous biomass. Biochar can be used as a
low-grade fuel, and also as a soil additive for making the land fertile
along with simultaneous carbon sequestering. Use of rice husk
biochar to fertilize the rice field has been a common practice in Asia
since hundreds of years [240]. Adding biochar to soil replaces car-
bon, nitrogen and other of the plant nutrients that are worn out
from the land during multiple harvests. Carbon in biochar is highly
stable in the soil environment and can be sequestered for thou-
sands of years [241,242]. Mollinedo et al. [243] have demonstrated
the use of biochar to improve the water holding capacity of
different soils. In their study biochar treatments increased water
retention in soil up to 25% compared to soil with no added biochar.
Another important application of biochar is adsorption of metal
ions from waste water. The metal ion adsorption property of bio-
chars is more related to their surface properties than their specific
surface area. Mullen et al. [193] suggested that the presence of large
amounts of inorganic components in biochar as surface charged
species possibly lead to chemisorption phenomena.
Biochar can also be used to meet the heating requirements for
pyrolysis, or can be combusted separately for heating. The inter-
mediate pyrolysis unit developed by EBRI, ‘Pyroformer’ runs on the
thermal energy obtained from the char produced [149].
Table 7, presents the representative data of ultimate analysis of
bio-char obtained from different feedstock as reported in literature.
Ultimate analysis of lignite is also mentioned for comparison.
9. Non-condensable gases
The non-condensable products of the pyrolysis reaction mainly
involve gases, such as CO, CO2, CH4 and a few non-methane hy-
drocarbons [119]. Park et al. [119] obtained CO2 (56.08%) followed
by CO (28.56%), as the most abundant species in the pyrolysis
products obtained from wild reed at 520  C. The HHV of the biogas
produced in their experiment was 10.85 MJ/kg.
Yang et al. [125] suggested that the chemical composition of the
gaseous products depend on different chemical structures of
biomass components. Hemicellulose, with higher carboxyl content,
account for a higher CO2 yield. Cellulose displays a higher CO yield,
mainly attributed to the thermal cracking of carbonyl and carboxyl.

Table 7
Analysis of biochar obtained from different biomass feedstock.

Feed Stock C, % H, % N, % S, % O, % Ash, % HHV, MJ/kg Ref.

Lignite 59.05 4.54 1.32 1.09 16.72 17.28 23.55 [244]

Albizia 70.4 3.1 0.4 e 15.8 e 26.60 [100]
Almond shells 87.9 2.5 1.1 0.5 7.8 2.8 e [40]
Apricot stones 89.5 2.4 0.9 0.8 6.4 2.0 e [40]
Bamboo 76.67 1.69 0.57 0.28 5.81 8.70 30.03 [111]
Banana leaves 48.0 3.2 1.2 0.33 e 23.5 18.2 [58]
Beech 73.6 3.4 0.2 e 6.3 e 29.1 [100]
Cherry stones 84.0 2.2 1.0 0.4 12.4 4.2 e [40]
Corn cob 67.7 3.2 0.5 e 9.2 e 26.50 [100]
Corn stover 56.7 1.89 0.75 0.22 e 30.4 19.8 [58]
Eucalyptus 79.5 2.77 0.17 0.27 e 5.0 30.7 [58]
Garlic stem 60.70 0 1.32 0 37.98 0.27 17.72 [62]
Grape residues 68.48 2.62 2.05 0.11 16.53 e 23.83 [47]
Grape seeds 84.7 1.3 1.6 0.3 12.1 13.1 e [40]
Iroko 68.4 3.4 0.2 e 15.3 26.30 [100]
Nut shells 85.9 2.1 0.5 0.5 11.0 4.9 e [40]
Olive husk 78.68 2.83 0.98 0.032 12.88 e 28.26 [47]
Pepper stem 71.11 0 1.71 0 27.18 0.13 22.06 [62]
Rapeseed cake 54.90 2.14 4.97 0.35 20.04 17.60 25.30 [200]
Red oak bark 86.72 2.8 0.59 0.00 9.89 e 33.12 [228]
Rice husk 51.52 2.14 0.46 0.021 9.77 e 18.73 [47]
Rice straw 67.89 1.50 1.12 0.28 8.96 e e [180]
Spruce 72.9 3.3 0.2 e 12.8 e 28.0 [100]
Sugar cane 41.3 2.9 0.40 0.10 e 33.8 14.15 [58]
Switch grass 87.23 2.71 1.33 0.00 8.73 e 33.94 [228]
Wheat straw 64.27 2.39 0.48 0.30 14.31 e 22.66 [47]
White oak 78.1 3.3 0.2 e 18.5 e 27.8 [245]
Wild reed 76.97 4.44 16.43 2.16 0 e 31.25 [119]
Wood chips 85.79 2.94 2.13 0.06 9.08 e 32.44 [228]
710 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716
With a higher presence of aromatic ring and methoxyl functional
groups, the pyrolysis of lignin releases much more H2 and CH4.
The non-condensable gases (NCG) can be usefully recycled back
into the reactor to support the fluidization or could be combusted
to provide process heat for large scale operations. Mante et al. [246]
studied the effect of recycling of NCG in the catalytic pyrolysis of
hybrid poplar. It was observed that recycling increased the liquid
yield, and simultaneously decreased the yield of char. The 13C NMR
analysis showed that recycling of NCG increases the aromatic
fractions and decreases the methoxy, carboxylic and sugar frac-
tions. Recycling of NCG increased the higher heating value and the
pH of the bio-oil as well as decreased the viscosity, oxygen content,
and density. More study is required for finding the optimum utili-
zation of the NCG.
10. Energy perspective
The gross calorific values of the bio-oils obtained from pyrolysis
of lignocellulosic biomass are comparable to those of oxygenated
fuels, such as methanol (23 MJ/kg) and ethanol (29.7 MJ/kg); while
the gross calorific values of bio-char are comparable to those of
lignite (15e27 MJ/kg). These products of pyrolysis can be used for
power generation [247]. However, the heating value of the bio-oil is
highly dependent on the nature of feedstock, source, pre-
processing and reaction conditions.
Beis et al. [248] reported a calorific value of 41 MJ/kg for the bio-
oil (44% yield) obtained from the pyrolysis of safflower seeds.
€
Ozçimen and Karaosmanog lu [200] reported a calorific value of
36.4 MJ/kg of the bio-oil (59.7% yield) obtained from the pyrolysis
of rapeseed. Gang et al. [249] reported of bio-oil (31% yield) from
pyrolysis of waste bamboo at 500  C in a fluidized bed reactor, with
a gross calorific value of 27.7 MJ/kg. Relatively less calorific values
are observed in the pyrolysis of wood biomass. Solantausta et al.
[162] reported a heating value of 17.5 MJ/kg for the bio-oil (65e70%
yield) obtained from pyrolysis of hardwood. The HHV values as
high as 21e30 MJ/kg for bio-char from corn cob have been reported
[193].
The cost of production is an important factor that decides the
fate of any process on the substantial scale. The studies on eco-
nomic analysis of bio-oil production, conducted in 80's and early
90's, by Scott and Piskorz [250], Beckman et al. [251], Cottam and
Bridgwater [252], Freel et al. [253], and Solantausta et al. [162] gave
the cost of production of bio-oil higher than the cost of light fuel oil
at that time, by a factor of 1.09e2.7. Biomass prices have a strong
influence on the economics of the process [247]. The cost of pro-
duction is not only a function of feedstock, and process conditions,
but also dependent on the scale of operation. Solantausta et al.
[162] reported ~18% decrease in cost of bio-oil production when the
plant capacity was increased by a factor of ~1.5.
The thermal efficiency of the system is a major factor in
lowering the cost of operation. Using biochar and NHG for
providing heat of operation can significantly increase the thermal
efficiency of the process. Halouani and Farhat [254], demonstrated
a pilot plant of wood biomass carbonization coupled with a pro-
vision for incineration of non-condensable smoke. The thermal
efficiency of the system increased from 42.33% to 89.51%, when
carbonization was performed using the heat of smoke incineration.
A method of bio-oil production, using the waste heat from blast
furnace slag has also been demonstrated by Luo et al. [255].
Do and Lim [256] performed a techno-economic comparison of
three plant models: (1) Bioethanol and jet fuel production plant, (2)
Gasification plant for combined heat and power, and (3) Fast py-
rolysis and bio-oil upgrading plant. In their study, it was concluded
that fast pyrolysis and bio-oil upgrading are the most promising
plant model because of high economic potential.
11. Challenges and opportunities
Despite several advantages of pyrolysis for biomass conversion,
efficient utilization of bio-oils as a transport fuel has not been
achieved on a substantial scale. Poor fuel characteristics, chemical
complexity, and instability of the bio-oils create a significant gap
between them and conventional fossil fuels. It is generally believed
that commercialization of pyrolytic biofuels hinges on improving
quality and stability of the bio-oil. Some of the principal challenges
incurred in using pyrolytic biofuels as a substitute for petroleum
oils, along with the potential solutions for each problem are
described as under:
11.1. Challenges with the feedstock
Although pyrolysis processes accept variable feed, the varying
nature of the feedstock leads to inconsistency in the product
behavior. The scale-up from the laboratory research to industrial
pilot plants becomes difficult with this inconsistency. Methods of
harvest and collection of biomass also alter the quality of the
feedstock. Establishment of standards for feedstock quality can help
in avoiding this inconsistency to some extent. The standards can be
in terms of acceptable moisture, in-homogeneity, dirt, and LHV.
Feed standardization is more important when the objective of
operation is to produce industrially important chemicals. Use of
dedicated energy crops hybridized to improve the liquid yield and
heating values is also an attractive solution.
Ash content of the biomass is also a problem. The inorganics
present in the ash, especially potassium and calcium, catalyze
biomass decomposition and char-forming reactions. Zhou et al. [257]
reported a strong catalytic effect of potassium on co-pyrolytic ki-
netics of wood biomass and low density polyethylene (WS/LDPE),
leading to decrease in peak decomposition temperature values.
Meanwhile, an increase in char yield was found for all the potassium-
treated WS/LDPE mixtures. The results from kinetic analysis showed
an increasing trend for activation energy and pre-exponential factor
with increasing potassium concentration in the first stage of
decomposition, followed by a decreasing trend in the second stage.
Some of the char formed in these reactions eventually ends up in the
bio-oil as suspended submicron particles. The presence of high
concentrations of submicron char particles in bio-oil, can make it
challenging for combustion machinery, because of the potential
release of the ash and alkali metals during combustion [75].
Deashing of original biomass via treatment with mild acids has
been in literature for improving the bio-oil quality [259]. Deashing
has also been demonstrated for increasing the rate of release of
volatiles. Consequently, the residence time available for volatiles
inside the biomass particles decreases, also minimizing the sec-
ondary reactions. This results in more higher-molecular-weight
products available for condensation into bio-oil, giving higher
liquid yield with high heating value. However, the heating value is
perceptibly decreased [260]. Raveendran et al. [42] studied the
pyrolysis of twelve different biomass feedstock and observed that
the yield of pyrolysis vapors, devolatilization rate and the initial
decomposition temperature increased whereas the char yield
decreased on demineralization of the biomass samples.
11.2. Complications in processing
For efficient pyrolysis to take place, and especially for fast py-
rolysis where high heating rates are required, heat transfer inside
the biomass poses a challenge. Since biomass has a low thermal
conductivity, it needs to undergo size reduction or comminution
before feeding into the reactor. The power requirement for me-
chanical comminution of biomass depends on the final particle size
 V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716
and biomass characteristics [261]. Choi et al. [25] demonstrated a
decline in bio-oil yield from 55.7 to 47.9%, when feed particle size
was increased from 0.5 to 2.5 mm.
Ablative reactors are exempted from such particle size
requirement. In these reactors, simultaneous pyrolysis reaction
along with the simultaneous erosion of char layer takes place, thus
ensuring unhindered heat transfer.
Conventional heating methods using tube furnace or fluidized
bed reactor are widely used for pyrolysis of biomass; however,
these external heating methods consumed long heating duration
that results in low-quality products due to the secondary reactions.
Other disadvantages including more energy required for the heat-
ing process, heat transfer resistance and heat losses to the sur-
rounding. Recently microwave pyrolysis was developed as an
alternative heating source for pyrolysis process to overcome these
problems. As a rapid pyrolysis process, microwave pyrolysis pre-
vents the formation of secondary reaction thus improved the
quality of products produced. It also provides a uniform heating of
the sample due to volumetric heating of the materials [112]. In the
more recent works, pyrolysis assisted with solar heating was
studied by Zeng et al. [262]. Integration of solar energy with py-
rolysis is expected to lower the cost of operation.
11.3. Product adversity
Bio-oil from pyrolysis has a number of disadvantageous char-
acteristics, which require consideration when intended to use the
oil as fuel. These characteristics prove to be undesirable in the
production, storage, transport, upgradation and utilization.
Moisture in bio-oil is also an undesirable fraction, as it lowers
the heating value and flame temperature; it contributes to increase
in ignition delay and is also known to lowers the combustion rates
[199]. Presence of moisture in biofuel can lead to low calorific value
and in-homogeneity in the liquid. In-homogeneity in biofuel leads
to layering or partial separation of phases, and filtration problems.
Because of the reactivity of the oxygenated functional groups, the
bio-oil has thermal instability and storage difficulties [263].
Polymerization or deterioration of the liquid can take place at
temperatures around 100  C, which can adversely affect physical
properties of the bio-oil such as viscosity, phase separation, and
carbonaceous deposition. Solid coke like products may form as the
result of these polymerization reactions, during distillation of the
oil. Condensation reactions such as etherification and esterification
may taking place during the storage of bio-oil, not only lead to the
formation of heavier compounds, but also increase the already
undesirable moisture content [206].
Low pH values attributed to the presence of organic acid com-
pounds (e.g. acetic and formic acids) in the bio-oil can cause
corrosion of the vessel and the pipework. These oils are corrosive to
conventional building materials such as carbon steel and
aluminum. Use of Polyolefins as the construction material, where
other circumstances permit has been recommended in the litera-
ture [264]. Bridgwater concluded mild steel as not suitable for
handling or storage of such fuel, and suggested polypropylene
piping to overcome problem [265].
Ash is an undesirable component of the bio-oil, which can lead
to erosion, corrosion and kicking problems in the engines and
valves. The ash problem becomes more important when the ash
content of the fuel is higher than 0.1%. Sodium, potassium and
vanadium compounds in the ash are responsible for high temper-
ature corrosion and deposition, while calcium is responsible for
hard deposits [258]. Ash in the entrained char is also believed to
catalyze the polymerization reactions in the bio-oil, thus increasing
its viscosity [259].
The presence of suspended char in the bio-oil can cause
711
problems such as erosion and equipment blockage. Suspended char
can also lead to slow rates of combustion, or occurrence of “spar-
klers” in combustion, leading to potential deposits or high carbon
monoxide emission. Char is also known to exhibit catalytic activity,
leading to potential cracking of bio-oil components and reduction
of condensable yield up to 20% [146]. Hot vapor filtration can be
used to overcome this challenge. Increase in combustion rate, lower
ignition delay, and low average molecular weight of the bio-oil has
been demonstrated by removal of suspended char via hot vapor
filtration [266].
High viscosity of the biofuel can lead to high pressure drops in
the pipelines leading to higher equipment cost and also the pos-
sibilities of leakage or even pipe rupture. High fuel viscosity leads to
poor flow characteristics and combustion properties.
Catalytic upgradation of bio-oil can help overcome most of these
challenges. Ghodke et al. [197] studied esterification of the bio-oil
obtained from babul wood pyrolysis with 1-butanol using
Amberlyst-15, as a solid catalyst for increasing the stability. The ester
formation significantly reduced the acidity and viscosity of the bio-
oil. The water released as byproduct of esterification was further
removed by reactive distillation. However, catalysts deactivation by
polymerization of furfural was identified as a key challenge. More
work on catalytic upgradation of bio-oils to improve its fuel char-
acteristics have already been cited in section 7.4.
Integrated bio-oil and upgradation processes, with catalyst
regeneration are attractive options. The Gas Technology Institute,
Birmingham, AL has developed and demonstrated at the pilot scale
based on the concept of integrated hydropyrolysis-
hydroconversion (IH2®) a new catalytic technology for the direct
thermochemical conversion of woody biomass directly into
blendstocks, gasoline, and diesel fuels. In this concept, hydro-
pyrolysis is been carried out under high pressures of hydrogen
(5e40 bar) and the vapors are in-situ hydrodeoxygenated to pro-
duce fuels [267].
12. Conclusions
Pyrolysis of lignocellulosic biomass has a potential to provide
environmental friendly future fuels/chemicals. The potential of bio-
oil is increasingly being acknowledged, leading to identification of
several ideal lignocellulosic species as feedstock for pyrolysis,
including wood biomass, agricultural residues, and dedicated en-
ergy crops. Various reactor configurations have also been studied
and are being modified to implement high efficiency. However,
presence of moisture in the biomass, uneven distribution, and
varying nature of the feedstock, lead to production of bio-oil which
is inferior in quality in comparison with the conventional fossil
fuels. Presence of oxygen, acidic compounds, and instability in the
bio-oil are some of the other major concerns in establishment of
pyrolysis on substantial scale. Research in the field of bio-oil
upgradation, production of high energy feedstock, and process
intensification as a bio-refinery to lower the cost of production can
help in overcoming these challenges. The successful and sustain-
able utilization of pyrolytic oils for substituting the fossil fuels will
depend on development of integral bio-refineries having a supply
of quality feedstock, cheap and easy-to-regenerate catalysts for bio-
oil upgradation, reactors with high thermal efficiencies, and
adapting energy market.
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