Renewable Energy Paper

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

following the ways to procure energy:
With the depleting fossil fuel resources, increasing environ-
mental concerns, and political commitment, research has been (a) Direct combustion to produce heat. The heat generated by
growing in the field of alternate energy sources. The UN climate this method must be exploited immediately for heating or
panel has aimed for a reduction in greenhouse gas emission by power generation. Other than the obvious problem of low
50e80% by 2050 [1]. To realize this target, it is essential to shift the efficiency, this approach also leads to undesirable ash
dependency from fossil fuels to the renewable energy sources. The buildup. The huge amount of CO2, produced as a by-product
renewable resources are inherently conceived using the energy of combustion is also a significant disadvantage.
present in sunlight and its direct and indirect impacts on the Earth (b) Conversion of biomass into biofuels and valuable hydrocar-
(falling water, heating effects, photons, plant growth, wind, etc.), bons using thermochemical or biochemical routes.
gravitational forces (the tides), and the heat of the Earth's core
(geothermal). These resources represent a gigantic underexploited Biofuels are the liquids or gases produced from biomass, which
capital of energy, which can meet much of the growing energy can be burned for obtaining energy. The first generation of biofuels
demand at prices less than those of conventional fossil fuels if comprised of biodiesel and bioethanol produced from different
provided adequate support. biomass such as edible and non-edible crops, agricultural wastes,
Biomass is the generic term for the plant (phytomass) and ani- and aquatic plants. The second generation of biofuels will be based
mal (zoomass) biomass. Lignocellulosic biomass refers to dry plant on biomass resources processed from integrated bio-refineries,
matter, which is an abundant and low-cost source of renewable covering not only the production of biofuels, heat, and electricity,
energy. It is significantly cheaper than the conventional fuel on an but also biomaterials [3]. Despite having a low carbon content,
energy basis. On agricultural land, the growth rate of lignocellulosic biofuels are environment-friendly, as they have negligible content
biomass on a per energy basis is 30e240 Barrel of oil equivalent per 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].
* Corresponding author. Thermo-catalytic Processes Area (TPA), Bio-Fuels Divi-
sion (BFD), CSIR-Indian Institute of Petroleum (IIP), Dehradun 248005, India.
‘Thermochemical processing’ of biomass uses heat and catalysts
E-mail address: tbhaskar@iip.res.in (T. Bhaskar). 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 along with its analysis has also been addressed in the later sections,
biomass, which uses enzymes and microorganisms for the same with more stress being laid on bio-oil and its upgradation. Since
purpose. Biomass conversion via biochemical route is often pyrolysis is still in its developing stage, many challenges stand in
considered as ‘mature’ technology with little scope for improve- the way of substantial implementation of the process. However,
ment [6]. In comparison with biochemical processes, thermo- each challenge provides a room for improvement and an oppor-
chemical processes occur faster (in a few seconds to hours); tunity for advancement. These challenges have been presented in
whereas the former takes time (in the range of days) to complete. the last sections of this article, along with potential solutions that
Also, unlike the biochemical processes, which produce lignin as a will determine the fate of pyrolysis.
by-product and face difficulty in fermenting the C5 sugars, ther- It has been the best interest of the authors to embed this article
mochemical methods of conversion utilize the whole feedstock to with references to the valuable research work, which have been
produce value-added hydrocarbons. Another advantage of ther- done in the field of pyrolysis of lignocellulosic biomass.
mochemical methods of conversion is that they are not feedstock
specific and can even process the combinations of feedstocks. 2. Lignocellulosic biomass
Gasification and pyrolysis are two of the most researched pro-
cesses for thermochemical biomass conversion. Gasification pro- Lignocellulosic biomass is typically composed of three main
vides fuel gas that can be combusted for heat generation, while building blocks: cellulose, hemicellulose, and lignin.
pyrolysis yields a liquid fuel that can substitute for fuel oil in any
static heating or electricity generation application. Pyrolysis is 2.1. Cellulose
thermal decomposition of a feed substance into smaller fragments
by heating in the absence of oxygen. The main benefit of pyrolysis Cellulose (Fig. 1(a)) is the most abundant organic polymer,
process over gasification is that the liquid fuel produced can be present in the cell wall of the plant cells; and almost in the pure
easily stored and transported. form in the cotton fibers. It is a natural polymer of repeating D-
Conversion of solid biomass to liquid fuel is desirable as it in- glucose units, a six-carbon ring, also known as pyranose. The three
creases the volumetric heat content, decreases the cost of trans- hydroxyl groups in each pyranose ring can interact with one
portation, and also enables them to be used in existing equipment another forming intra- and intermolecular hydrogen bonds which
(oil boilers, etc.). Although the thermal decomposition of organic give cellulose a crystalline structure, and its unique properties of
materials for the production of valuable liquid hydrocarbons, has mechanical strength and chemical stability. The pyranose rings are
been investigated since centuries, the interest in pyrolysis for linked to each other by acetal bonds (eOe, b-1,4-glycoside linkage)
production of biofuels emerged less than 40 years back [7]. between C-1 of one pyranose ring and C-4 of the succeeding ring.
Different reactor configurations such as vortex reactor, rotating Since a molecule of water is lost in such linkage, cellulose can also
blade reactor, rotating cone reactor, vacuum reactor, and bubbling be defined as a polysaccharide of anhydroglucopyranose [9].
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 2.2. Hemicellulose
Spain, Italy, UK, Canada, Finland, and Netherland [8].
In this review article, a thorough comprehension has been Hemicellulose (Fig. 1(b)) surrounds the cellulose fibers and
presented on the pyrolysis process as a paramount thermochemical stands as a connecting link between cellulose and lignin. It is a
biomass conversion technique. Lignocellulosic biomass, which is an heterogeneous group of branched polysaccharides. Different
ideally suited feedstock for pyrolysis has been discussed, for its monomers such as glucose, galactose, mannose, xylose, arabinose
composition, categorization, and characterization. Different kinds and glucuronic acid, are the structural elements of hemicellulose.
of pyrolysis and reactor configurations to execute them have been The degree of polymerization (DP) of hemicellulose is 50e200
addressed in the subsequent sections. The product distribution, monomers, which is much lower than that of cellulose [10]. While
Fig. 1. Components of lignocellulosic biomass: (a) cellulose, (b) structure monomers of hemicellulose, and (c) lignin.
V. Dhyani, T. Bhaskar / Renewable Energy 129 (2018) 695e716 697
cellulose has a hydrolysis-resistant crystalline structure, hemi- 3.1. Wood biomass

cellulose is amorphous, with little physical strength. It is readily
hydrolyzed by dilute acids or bases, as well as hemicellulose Various kinds of wood-based biomass have been used for py-
enzymes. rolysis. Different softwoods that have been studied include cedar
[19], douglas fir [20], pine [21,22], redwood [23], and spruce [21,24].
2.3. Lignin The hardwood varieties that have been majorly studied are bald
cypress [25], beech [23,26], birch [27,28], blackbutt [29], chestnut
Lignin (Fig. 1(c)) is an aromatic, three-dimensional and cross- [23], eucalyptus [19], hybrid poplar [30,31], and oak [19,32]. Wood
linked phenol polymer that consists of a random assortment of waste including sawdust [33,34], particle board [35], waste from
differently bonded “hydroxyl-” and “methoxy-” substituted furniture factories and other wood processing industries [36] has
phenylpropane units. These phenylpropane monomers can be also been studied by several research groups.
categorized as guaiacyl, syringyl and p-hydroxylphenyl units
[11,12]. Lignin is mainly present in the outer layer of the fibers 3.2. Agricultural waste
and is responsible for the structural rigidity, and holding the fi-
bers of polysaccharides together. Lignin percentage may vary Pyrolysis of agricultural waste is desirable, as the cultivation of
from 23 to 33% in softwoods to 16e25% in hardwoods. For the agricultural crops has less demand of area and cultivation period,
lignocellulosic biomass, lignin percentage up to 40% has been compared to wood biomass. Also, a large part of the crop body is
reported. Physically, cellulose microfibrils are coated with non-edible and goes as waste. Straw makes up as much as 50% of
hemicellulose, whose empty spaces are filled up with lignin [13]. the yield of cereal crops and has more potential for char production
Lignin plays a binding role between hemicellulose and cellulose compared to wood [37].
within the cell wall. Different varieties of agricultural wastes that have been tested
The specific structure of lignin varies with the parent biomass for pyrolysis include ‘shells’ (cotton cocoon [38,39], almond [40,41],
and may also show differences based on the extraction method. ground nut [42], hazelnut [43e45], nut [40], oil palm [46], etc.),
Softwood and hardwood lignin have dissimilar structures. husks (olive [39,47], rice [48,49], etc.), ‘stover’ (corn [30]), ‘stalk’
“Guaiacyl” lignin, which is predominantly found in softwoods, is a (corn [50], cotton [51], rape [52], etc.), ‘straws’ (corn [50], cotton
polymer of higher fraction of coniferyl phenylpropane units. On the [51], rape [52], wheat [50], etc.), and ‘non-edible seeds’ (babool
other hand, “Guaiacyl-syringyl” lignin, which is typically found in [53], grape [40], karanja [54], linseed [54], mahua [54], niger [54],
hardwoods, is a copolymer of both the coniferyl and sinapyl phe- rape [55,56], etc.). Pyrolysis of other agricultural wastes, like apricot
nylpropane units. The fraction of sinapyl units in hardwoods is stones [40], bagasse [27,57], banana leaves [58], bocaiuva residues
higher than that in softwood lignin [14,15]. Due to the presence of [59], cherry stones [40], coir pith [12], cotton seed cake [60,61],
both guaiacyl and syringyl units, the hardwood lignin has higher garlic stem [62], grape residue [47], jatropa residue [63,64], jute
methoxyl content, compared to the softwood lignin, which is sticks [65], olive waste [66,67], pepper stem [62], safflower seeds,
composed of guaiacyl units only [16]. sorghum bagasse [68], sunflower bagasse [69], tea waste [39], and
Other than these three components, biomass also comprises of tobacco waste [68], has also been reported in literature.
some extractives and inorganic components. Extractives include One of the major concerns with use of agricultural residue as
alkaloids, essential oils, fats, glycosides, gums, mucilages, pectins, feedstock for pyrolysis is that farmers and landowners control the
phenolics, proteins, resins, saponins, simple sugars, starches, ter- supply of biomass. Not only is the bulky agricultural residue limited
penes, and waxes. These can be extracted from biomass using polar to a local market due to transport costs, the composition of feed-
(alcohol, methylene chloride, or water) or nonpolar solvents (hex- stock is also inconsistent and variable. The feedstock from farms is
ane or toluene). Extractives function as intermediates in meta- also susceptible to dirt in the biomass, which can lead to equipment
bolism, as energy reserves, and as plant defenses against microbial wear and increased maintenance cost [70].
and insect attack [15]. The inorganic components are present as ash
in the biomass and are addressed in section 4.4. 3.3. Energy crops
3. Feedstock for pyrolysis Certain crops of high energy values, such as bamboo [71], sor-
ghum [72] and many varieties of grasses have also been studied for
The availability of industrial quantities of lignocellulosic pyrolysis. Energy crops cut the competition for fertile land as they
biomass is a necessity for the establishment of any biorefinery. An can be grown on land that is not suitable for agricultural crops.
abundant supply of renewable feedstock is globally available for Bamboo is a class of more than 1250 species of fast growing, large
being converted into biofuels, such as agricultural crops, residues, woody grasses, found abundant in Asia. Lignin content as high as
forestry materials, and algal biomass. Dedicated energy crops such 29% has been reported in some of the bamboo species [73].
as sorghum and several varieties of grasses; and municipal solid Sorghum is a genus of grasses found in parts of Asia and Africa.
waste (MSW) are also attracting attention. As per a macro level Raw sweet sorghum comprises of 14e16% lignin on a dry basis. It is
study in the US alone, the annual supply potential of dry agricul- of interest as a dedicated agricultural energy crop because of its
tural and forest biomass is 900 and 400 million tons respectively, drought tolerance, relatively low input requirements (water and
which is sufficient to replace more than 30% of the current trans- manure), and ability to produce high yields under a wide range of
port fuel use [17]. However, not all biomass are suitable for being environmental conditions. Sweet sorghum comprises of large sugar
converted into liquid fuels and appropriate selection of feedstock content in the crop that can be converted to ethanol, while the
for thermochemical conversion is necessary for process optimiza- bagasse can be easily used a feedstock for thermochemical con-
tion. Ganesh [18] developed criteria for evaluating the suitability of version processes [72].
biomass for a conversion process to obtain solid, liquid and gaseous Grasses are usually rich in hemicellulose. Typical grasses may
fuels. In his method, the Rating Indices (RI) of different biomass comprise of 25e40% cellulose, 35e50% hemicellulose and 10e30%
were calculated using the yield, HHV, and ultimate analysis data. lignin [74]. Several genus of grass family such as bermuda grass,
These RI allowed the ranking of the tested biomass for gasification, elephant grass, esparto grass, switch grass [30,75] etc. have been
carbonization and liquefaction operations. used as feedstock for pyrolysis by different researchers. Parrish and
Fike [76] mentioned that switchgrass can be grown on soils of analysis data of about 300 biomass samples in their handbook
moderate fertility without fertilizing, or with limited additions of “Thermal Data for Natural and Synthetic Fuels”.
fertilizer, and still maintain productivity.
Use of dedicated energy crop as a feedstock will require change 4.3. Fiber analysis
in current production and crop management practices. A reliable
market will be needed for the farmer to commit to producing such The quantity of individual lignocellulosic fractions in a biomass
biomass. sample can be found by numerous wet chemical analytical
Other than the above mentioned biomass, pyrolysis of feedstock methods via determination of Neutral Detergent Fiber (NDF), Acid
such as aquatic biomass [77e81], cattle manure [82], household Detergent Fiber (ADF) and Acid Detergent Lignin (ADL) [92e94].
waste [83,84], municipal solid waste [84,85], oil shale [86], poultry These analytical procedures are standardized by the American So-
litter [87], sewage sludge [24] and used oils [88] has also been re- ciety for Testing and Materials (ASTM) and the Technical Associa-
ported in literature. tion of the Pulp and Paper Industry (TAPPI). NDF is obtained by
stripping the starch and extractives from the biomass sample,
4. Feedstock analysis leaving cellulose, hemicellulose and lignin. ADF is obtained by
removal of hemicellulose from the sample. On removal of cellulose
Analysis of biomass is an imperative step in order to assess its from ADF, ADL is obtained. The values of hemicellulose and cellu-
value as feedstock for pyrolysis, determining the reaction condi- lose are obtained by difference in the values of NDF, ADF and ADL
tions, and predicting the product behavior. [95]. Table 1 presents the lignocellulosic composition, as well as
proximate and ultimate analysis of different biomass as reported in
4.1. Proximate analysis the literature.
The ratio of the three constituents, depend on the nature of
The simplest and most commonly used analysis technique is biomass and the part of the plant being sampled. For example,
proximate analysis. Proximate analysis is performed to determine hazelnut shell contains up to 51.3% lignin [96] while tree leaves are
the four essential feedstock fractions: (a) moisture, (b) volatile lignin-free [97]. Lignin content in cotton cocoon shell is 48.7% [98],
matter, consisting of the components of biomass, except for water, while its seed hair has no lignin [12].
which are liberated as gases and vapors at high temperature in the
absence of oxygen, (c) fixed carbon, the non-volatile fraction of 4.4. Inorganic metals in feedstock
biomass, and (d) ash, the inorganic residue the remains after
combustion. Inorganics compounds are present as ash in the biomass feed-
Biomass with high volatile matter has highest conversion, in stock. The main inorganic constituents being compounds of po-
comparison to biomass with high fixed carbon. Theoretically, tassium, calcium, sodium, silicon, phosphorus, and chlorines.
biomass with higher volatile fraction may be suitable for produc- Inductively coupled plasma mass spectrometry (ICP-MS), and
tion of bio-oil, while the one with higher fixed carbon may be more inductively coupled plasma atomic/optical emission spectroscopy
suitable for production of bio-char. Table 1 presents the literature (ICP-AES/OES) are commonly used techniques reported in literature
survey of proximate analysis of different biomass feedstock. for determination of inorganic content in biomass. Table 2 presents
the literature survey of the elemental analysis of inorganics in some
4.2. Ultimate analysis of the biomass feedstock.
The composition of ash in bio-mass ranges from less than 2% in
Ultimate analysis test produces more comprehensive results softwoods to as much as 15% in herbaceous biomass and agricul-
than the proximate analysis. It involves determining the carbon, tural residues (see Table 1).
hydrogen, nitrogen, sulphur and oxygen (CHNSO) in the material.
The ratio of these elements obtained from ultimate analysis provide 4.5. Thermal analysis
a better comparison among the feedstock. The results can also be
used for determination of heating value of the feedstock. Chaniwala Along with feedstock composition, knowledge of feedstock
and Parikh [89] developed following empirical correlation for decomposition behavior is also important for design of a pyrolysis
determination of higher heating value (HHV) of the biomass using process. The decomposition behavior of the biomass is studied
the elemental and proximate analysis: using thermal analysis, the commonly used techniques for which
involve, thermogravimetric analysis and differential scanning
HHV, MJ/kg ¼ 0.3491(C) þ 1.1783(H) e 0.10(S) e 0.0134(O) e calorimetry.
0.0151(N) e 0.0211(A) (1) Thermogravimetric analysis (TGA) is a technique in which
weight loss of a sample is measured with increasing temperature.
Friedl et al. [90] provided two correlations for calculation of TGA data can be used for, (1) material analysis by comparison with
HHV based on the data of ultimate analysis: an ordinary least characteristic decomposition patters, (2) formulation of reaction
squares regression (OLS) (Eq. (2)) and a partial least squares kinetics, (3) proximate analysis, (4) analysis of thermal stability, etc
regression (PLS) method (Eq. (3)). These equations were calibrated [124]. Carrier el al [95] demonstrated the use to TGA for determi-
using 122 different biomass samples and give the HHV on a dry nation of lignocellulosic composition of biomass.
basis. Fig. 2(a), shows TGA curves of pure cellulose, hemicellulose and
lignin samples. It can be observed that the three biopolymers
HHV, MJ/kg ¼ 1.87(C2) e 144(C) e decompose at distinct temperature spectrums. Hemicellulose starts
2802(H) þ 63.8(CH) þ 129(N) þ 20147 (2) an early decomposition, with most decomposition taking place in
the temperature range of 220e315 C. Decomposition of cellulose is
HHV, MJ/kg ¼ 5.22(C2) e 319(C) e mainly confined in the temperature range of 315e400 C, with very
1647(H) þ 38.6(CH) þ 133(N) þ 21028 (3) less solid residue remaining after 400 C. Among the three com-
ponents, lignin is the most difficult one to decompose. Its decom-
Gaur and Reed [91] have published the proximate and ultimate 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)
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. Brys 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.
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,

which can be achieved by finely grounding the feed biomass. The pyrolysis process that aims at increases the energy density and fuel
feed is heated at high temperatures (450e600 C) for short resi- properties of biomass [156]. During torrefaction process, the water
dence times (typically less than 2 s). Liquid yield as high as 75% on contained in the biomass, as well as superfluous volatiles, are
dry feed basis has been reported for fast pyrolysis of wood removed, while the biopolymers (cellulose, hemicelluloses, and
[147,148]. Since, the reaction takes place for a very short duration, lignin) partly decompose by giving off organic volatiles [118]. The
not only chemical kinetics, but also rate of heat and mass transfer, end product is the residual solid, dry, blackened material which is
and transition phenomena play a crucial role in determining the termed as “torrefied biomass” or “bio-coal”. The product is free
product chemistry. Desirable products can be produced by setting from volatiles and has much higher energy density than the parent
process parameters at optimum [147]. biomass. The decrease in weight and volume of the biomass also
enables its easy transportation over long distances to plants for use
5.2. Intermediate pyrolysis or further processing. Torrefied biomass is also hydrophobic,
meaning it can be stored for long time durations without absorbing
Intermediate pyrolysis is carried out in the temperature range of water. Torrefied biomass also requires less energy to crush, grind, or
300e500 C. Compared to fast pyrolysis, the liquid products ob- pulverize; and the same tools as for crushing coal can be used
tained from intermediate pyrolysis have low tar yield and viscosity. [118,157].
More controlled chemical reactions take place, and thus the reac-
tion conditions in intermediate pyrolysis offer a broad range of 5.4. Hydropyrolysis
variation for process optimization. Although lower liquid yields (up
to 55%) are obtained in this operation, large biomass sizes (coarse, Other than the inert nitrogen environment for pyrolysis, py-
shredded, chopped or ground) are acceptable [147]. rolysis in reductive hydrogen environment has also been studied by
An intermediate pyrolysis reactor (Pyroformer), operating in the several researchers. In hydropyrolysis, as the reaction takes place
temperature range of 400e500 C, has been developed by Euro- under the pressures of hydrogen, the formation of free radicals is
pean Bioenergy Research Institute (EBRI) at Aston University. The hindered. The amount of unsaturated hydrocarbons reduces
unit is driven by the thermal energy obtained from the char pro- thereby increasing the quality of the bio-oil formed. The probable
duced [149]. reaction mechanism under nitrogen environment could be the
random thermal cracking of the large biomass molecule which
5.3. Slow pyrolysis leads to an increased variation in the products formed. However, in
the presence of hydrogen, it could be the systematic bond cleavage
Slow pyrolysis is a batch process which is carried out at low (initiation with hydrogenolysis/hydrogenation, bond breaking in
temperatures and slow heating rates, for long residence times. This the order of increasing bond strength and stability of formed
process is more tolerant to the moisture content in the feedstock. components) in the macromolecular structure which leads to the
Although most literature present in slow pyrolysis is based on its formation of few products with higher selectivity [34,158].
use for production of solid fuel, liquid fuels can also be produced Putun et al. [69] reported a 40% increase in the bio-oil yield
from this operation [150]. Carbonization is the slow pyrolysis of when pyrolysis of sunflower bagasse was conducted under
biomass without condensing the pyrolysis products. It is the oldest hydrogen pressure (150 bar). Balagurumurthy et al. [159] studied
technique of treatment of biomass for the production of charcoal; the pyrolysis of rice straw under hydrogen and nitrogen environ-
and is carried out where biochar is the desired product. The vapors ments and showed that the reaction mechanism is different in both
are usually not condensed in this operation but can be used for cases as the product portfolio was different in the two atmospheres.
providing the heat for operation, by direct or indirect heating. The bio-oils obtained under hydrogen atmosphere showed more
Heating rates as low as 0.1e2 C, have been reported [151]. Mois- selectivity towards phenolic compounds. Although the higher yield
ture affects the char properties, which are helpful in producing of bio-oil was obtained under the nitrogen atmosphere, the selec-
activated carbons through pyrolysis. Moisture content of 15e20% is tivity towards phenolic compounds was less [159].
typical for charcoal making [152,153]. The feed size can vary from An integrated gasification-hydropyrolysis process has been
briquette size to whole logs. Although, wood is the predominant developed and patented by Agarwal and Singh [160]. This low-cost,
feedstock for slow pyrolysis, other feedstock such as cashew nut process has been demonstrated for the production of high liquid
shells and palm have also been reported [154,155]. yields using H2 as well as the heat required for the biomass fast
Torrefaction is another slow pyrolysis operation, which is con- pyrolysis supplied by the syngas derived from gasification or
ducted in the temperature range of 225e300 C. It is a mild reforming of Carbon-Containing Moiety (CMM).
Fig. 2. Thermal analysis of biomass components: (a) TGA, (b) DSC.

6. Reactor configurations 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
A further level of complexity to the pyrolysis operation is added char particles. High throughput is the main advantage of CFBR. The
by the type of contact between particles in the reactor and depend heat for the process is gathered by burning the char for heating the
on the configuration of the pyrolysis reactor [103]. Some of the sand in a separate reactor unit, and recirculation of the hot sand
traditional reactor configurations that have been used for pyrolysis into the reactor [163].
are as follows.
6.2. Ablative reactors
6.1. Fluidized bed reactors
The mechanism of pyrolysis in the ablative reactors (Fig. 5) is
Fluidized bed reactors (FBR) are the most researched and one of similar to melting of butter on the surface of a frying pan. In these
the most successful pyrolysis reactors [30]. In these reactors, rapid reactors, the thermal “erosion” of the biomass takes place by
heating of biomass particles takes place by mixing them in a stream pressing against the hot reactor wall. The rate of reaction is strongly
of moving sand particles at high temperatures. The volatile mixing influenced by pressure, the relative velocity of the biomass on the
of sand with biomass particles leads to high heat and mass transfer heating surface, and the reactor surface temperature. This type of
coefficients, a favorable condition for fast pyrolysis. The bed is reactor accepts a feedstock of large sizes and allows good me-
heated by externally combusting the bio-oil/char produced, and chanical abrasion of char. In the 1980s, fundamental work on
transferring this heat to the bed directly (adding hot solids to the ablative pyrolysis reactors was done at CNRS in Nancy, France
bed) or indirectly (hot gas/steam passed through the tubes in the where research was carried out on the relationship between
bed). FBR also has a simpler design, easy scale-up, and proficient pressure, motion, and temperature [164]. Later, NREL (formerly
control over the residence time. However, large reactor size, and known as SERI) in Boulder, Colorado developed an ablative vortex
the high cost of construction and operation are the disadvantages reactor, in which the biomass was accelerated to supersonic ve-
[20]. locities to derive high tangential pressures inside a heated cylinder.
The FBR are mainly classified into three basic types: (a) However, the problem of insufficient biomass conversion, requiring
bubbling, (b) entrained, and (c) circulating. The fundamental theme recycling was observed in this work [165]. In the 1990s, Peacocke
in these reactors is that the biomass suspension sanctions a rapid and Bridgewater [162] (Aston University), successfully built and
thermochemical conversion. In the bubbling fluidized bed reactors operated a prototype rotating blade ablative reactor of capacity
(BFBR) (Fig. 3), the gas velocity is usually in the range of 1.5e2 times 3 kg/hr, with the liquid yield of 80%. In the continued work on
the minimum fluidization velocity. The entrained fluidized bed ablative cyclone reactors at CNRS, France, bio-oil yield up to 74% has
reactor (EFBR) operates at co-current flow, where the biomass been reported [166]. In Germany, ablative reactors of capacity
particles fall freely under gravity or entrained under the influence 250 kg/hr have been commissioned by Fraunhofer UMSICHT and
of gas drag force [147]. PYTEC, at Sulzbach-Rosenberg and Hamburg respectively. PYTEC
Fundamental studies on the FBR were carried out at the Uni- also plans for the demonstration of a pilot plant of capacity 2 ton/hr
versity of Waterloo, Canada, in the 1980s. Later, the corporate in Mecklenburg-Vorpommern [167,168].
commercialization of the FBR technology of the University was Some disadvantages of ablative reactors are [147]:
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 Fig. 4. Circulating fluidized bed reactor.
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. Fig. 5. Ablative pyrolysis reactor.

(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 Fig. 7. Auger/Screw pyrolysis reactor.
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. achieved in fluidized bed reactors, suggesting noteworthy possi-
A pilot plant based on the rotating cone reactor having a ca- bility of further improvements.
pacity of 2 tons per hour, has been installed by BTG in Malaysia. The A modular and transportable bio-oil plant based on auger
plant gets its feedstock, empty fruit bunches from a closely located reactor has been demonstrated by Renewable Oil International, LLC
palm mill [171]. (ROI), Florence, AL [172]. Another mobile pyrolysis technology
(Pyroformer™), based on intermediate pyrolysis in auger reactor
6.4. Auger/screw reactor has been developed by EBRI at Aston University. The pyrolysis va-
pors produced from Pyroformer™ are quenched using diesel as the
Auger (or screw) reactors (Fig. 7) are tubular, continuous re- quenching medium which is recirculated in a closed loop until the
actors in which solid biomass is transported via a rotating screw, required blend of pyrolysis liquid in diesel is reached. The mobile
while the heat required for pyrolysis is transported along the unit has been successfully demonstrated for providing continuous
tubular wall of the reactor. The screw thereby fulfills two purposes: power to a school in Khusapura village in India [174]. Some of the
first, it mixes the feed and second, it controls the residence time of popular pyrolysis units installed worldwide are tabulated in
the biomass in the reactor. An essential advantage of this reactor Table 3.
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 7. Bio-oil from pyrolysis
biomass generation or where the biomass is abundantly available.
On-site conversion of biomass reduces the cost of operation, by Bio-oil is the term given to the dark brown, freely-flowing liquid
saving the cost of transport of feedstock to biorefinery [172]. Ingram obtained from pyrolysis of biomass. This liquid is not the product of
et al. [173] conducted fast pyrolysis of wood biomass in an auger thermodynamic equilibrium but is produced by rapid cooling or
reactor. It was observed that bio-oil produced in their work was quenching of the gaseous products. The liquid also comprises of
comparable to the bio-oils produced by fast pyrolysis in fluidized some fragments of cellulose, hemicellulose, and lignin, which were
bed and vacuum pyrolysis processes. However, lower heat transfer able to cross the pyrolysis environment by volatilization or by being
rates were observed in the process, in comparison with those 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
Fig. 6. Rotating cone pyrolysis reactor. solids, char, oxygen and acidic compounds. These constituents have
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].
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 methods reported in the literature for analysis of bio-oil include
the literature for different biomass. Proton nuclear magnetic resonance (1H NMR) and Fourier trans-
form infrared spectroscopy (FT-IR).
7.3. Bio-oil analysis Pyroprobe gas chromatography-mass spectrometer (Py-GC/MS)
is a state of art characterization technique for effective research in
Characterization of bio-oil is an attempt to find the composition the field of biomass pyrolysis. It enables an online analysis of the
through various analytical techniques. Gas chromatography-mass products of pyrolysiss reaction taking place in the pyroprobe and
spectrometry (GC/MS) is the most commonly used characteriza- thus identifying all evolved species over a particular temperature
tion method reported in the literature for analysis of the organic range [64,100,194,195].
fraction of the bio-oil. The GC section of the equipment separates A better comparison of bio-oils with diesel fuel can be made by
the individual components of the bio-oil mixture via volatilization comparing the elemental composition, and HHV of the two fuels. O/
of the mixture through GC column, followed by identification of C ratio of bio-oils is much higher than the conventional diesel fuels,
these components at MS. The popularly used GC columns for subsequently decreasing its heating value. Low N/C and S/C ratios
analysis of bio-oil as reported in the literature are, BP5 (5% Phenyl/ are desired in fuel for better emission control. Table 6 presents a
95% Dimethyl Polysiloxane) [192], DB-5ms (Phenyl Arylene poly- literature survey of elemental analysis of different bio-oils, in
mer) [5,78], and HP-5 ((5%-Phenyl)-methylpolysiloxane) [87]. For comparison with standard diesel fuel.
analysis of the aqueous fraction use of high-pressure liquid chro-
matography (HPLC) has been reported [193]. Other common
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

In hydrodeoxygenation (HDO), oxygen is removed from
Upgradation of pyrolysis vapors by various means, physical, oxygenated hydrocarbons by reaction with hydrogen at high
chemical, catalytic, etc., has been researched by several research pressures in the presence of a catalyst. Major studies conducted on
groups to improve bio-oil properties, and enable its usage as ‘fuel’. HDO, are based on model compounds found in bio-oil. Zhang et al.
Upgrading is desirable to reduce the oxygen content in the oil and [206] studied HDO of pyrolysis oils using cobalt molybdate catalyst
make it resemble crude oil. 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
7.4.1. Physical upgradation
mono- and dimethyl substituted phenols over sulfide cobalt
Hot vapor filtration is the most common method of physical
molybdate catalyst. Non-sulfided catalysts, such as Pt/SiO2/Al2O3
upgradation of bio-oil, by removal of ash from the organic vapors
[210], vanadium nitride [211], and Ru [212], have also been used for
before condensation. It can provide considerable ash reduction
HDO. A comprehensive review on the chemistry of HDO process has
compared to conventional cyclone separation. Decrease in the
been published by Furimsky [213].
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]. 7.4.3. Catalytic cracking of pyrolysis vapors
Agblevor and Bessler [75], used hot vapor filtration on the va- Catalysts can be used to improve the quality of the pyrolysis
pors produced in pyrolysis of switchgrass. It was observed that products, by two routes. One is catalytic upgradation of the bio-oil
although the yield of condensable didn't change, the bio-oil pro- as the downstream process, using metallic or bifunctional (hydro-
duced was not as dark as the oils from the cyclone separator, sug- genating and acidic) catalysts [214,215]. The other route comprises
gesting a decrease in the level of suspended char in the oil. of in-situ upgradation by integrated catalytic pyrolysis, in which the
Another method of physical upgradation is the addition of low catalyst is added into the pyrolysis system.
molecular weight solvents to the bio-oil. Solvents such as ethanol The vapors produced in the pyrolysis reaction undergo further
and methanol can considerably alter the viscosity and storage cracking inside the pores of the catalyst to form low molecular
stability of the oils. The addition of these solvents shifts the stoi- weight compounds. Although the yield of condensable organic
chiometry from polymers to oligomers which are stabilized by the compounds tends to decrease in this system, there is a significant
solvent groups [204]. Diebold [205] reported a 20 times decrease in increase in the product quality in terms of low oxygen content and
the rate of aging, by the addition of 10% methanol in the bio-oil. enhanced calorific value. Product selectivity is also an attractive
Although bio-oil is immiscible in diesel, an emulsion of the two feature of catalytic pyrolysis, the selectivity being dependent on
can be prepared using suitable emulsifying agents, in order to catalyst pore size and nature of active sites [216]. Several catalysts
improve the fuel characteristics of the bio-oil. Ji-lu [191] studied the such as AlMCM-41 [217], HY [195], HZSM-5 [218], silicalite [216], Y-
emulsions of bio-oil obtained from pyrolysis of rice husk in diesel, Zeolite [216], ZSM-5 [219], have been researched for integrated
in terms of LHV and acidity. As the bio-oil to diesel ratio was catalytic pyrolysis. Use of metal doped ZSM-5 catalysts (ZnZSM-5
increased from ~1:3 to ~3:1, LHV decreased from 34.55 to 23.65 MJ/ [220], MnZSM-5 [221] and GaZSM-5 [222]) has also been reported
kg, while pH shifted from 2.7 to 2.2. in the literature.
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]).
methoxypropenylphenol (isoeugenol), etc., have a significant eco- since hundreds of years [240]. Adding biochar to soil replaces car-
nomic potential, in food, pharmaceutical and paint industries bon, nitrogen and other of the plant nutrients that are worn out
[234,235]. Patel et al. [236] demonstrated a method of selective from the land during multiple harvests. Carbon in biochar is highly
extraction of phenols from the bio-oil produced from sugarcane stable in the soil environment and can be sequestered for thou-
bagasse pyrolysis by supercritical fluid extraction (SCFE) route. The sands of years [241,242]. Mollinedo et al. [243] have demonstrated
phenols and substituted phenols obtained after extraction can be the use of biochar to improve the water holding capacity of
used as natural phenols for preparing phenol-formaldehyde resins, different soils. In their study biochar treatments increased water
this reducing the dependence on petro-based phenols for resin retention in soil up to 25% compared to soil with no added biochar.
manufacturing. Another important application of biochar is adsorption of metal
Pavlath and Gregorski [237] pyrolyzed five carbohydrate prod- ions from waste water. The metal ion adsorption property of bio-
ucts (amylase, cellobiose, cellulose, glucose, and maltose) and chars is more related to their surface properties than their specific
showed that furfural and furfuryl alcohol up to 30% and 12e30% surface area. Mullen et al. [193] suggested that the presence of large
respectively were produced. Furfuryl alcohol is a useful chemical amounts of inorganic components in biochar as surface charged
intermediate in the manufacture of furan resin prepolymers, which species possibly lead to chemisorption phenomena.
are exploited in thermoset polymer matrix composites, cement, Biochar can also be used to meet the heating requirements for
adhesives, casting resins and coatings. Furfuryl alcohol is also used pyrolysis, or can be combusted separately for heating. The inter-
for the production of tetrahydrofurfuryl alcohol which is used as a mediate pyrolysis unit developed by EBRI, ‘Pyroformer’ runs on the
nonhazardous solvent in agricultural formulations and as an thermal energy obtained from the char produced [149].
adjuvant to help herbicides penetrate the leaf structure. Furfural is Table 7, presents the representative data of ultimate analysis of
an important chemical solvent which can be used to make other bio-char obtained from different feedstock as reported in literature.
furan chemicals, such as furoic acid, via oxidation, and furan itself Ultimate analysis of lignite is also mentioned for comparison.
via palladium catalyzed vapor-phase decarbonylation [238].
The aqueous phase of the bio-oil comprised of modest con-
9. Non-condensable gases
centrations (~3%) of calcium carboxylates including calcium acetate
and calcium formate. These salts have potential applications in
The non-condensable products of the pyrolysis reaction mainly
deicing, sulfur dioxide removal during fossil fuel combustion, and
involve gases, such as CO, CO2, CH4 and a few non-methane hy-
as a catalyst during coal combustion [239].
drocarbons [119]. Park et al. [119] obtained CO2 (56.08%) followed
by CO (28.56%), as the most abundant species in the pyrolysis
8. Biochar products obtained from wild reed at 520 C. The HHV of the biogas
produced in their experiment was 10.85 MJ/kg.
Biochar, charcoal or char, is the solid carbon-rich residue left Yang et al. [125] suggested that the chemical composition of the
after pyrolysis of carbonaceous biomass. Biochar can be used as a gaseous products depend on different chemical structures of
low-grade fuel, and also as a soil additive for making the land fertile biomass components. Hemicellulose, with higher carboxyl content,
along with simultaneous carbon sequestering. Use of rice husk account for a higher CO2 yield. Cellulose displays a higher CO yield,
biochar to fertilize the rice field has been a common practice in Asia 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]
With a higher presence of aromatic ring and methoxyl functional 11. Challenges and opportunities
groups, the pyrolysis of lignin releases much more H2 and CH4.
The non-condensable gases (NCG) can be usefully recycled back Despite several advantages of pyrolysis for biomass conversion,
into the reactor to support the fluidization or could be combusted efficient utilization of bio-oils as a transport fuel has not been
to provide process heat for large scale operations. Mante et al. [246] achieved on a substantial scale. Poor fuel characteristics, chemical
studied the effect of recycling of NCG in the catalytic pyrolysis of complexity, and instability of the bio-oils create a significant gap
hybrid poplar. It was observed that recycling increased the liquid between them and conventional fossil fuels. It is generally believed
yield, and simultaneously decreased the yield of char. The 13C NMR that commercialization of pyrolytic biofuels hinges on improving
analysis showed that recycling of NCG increases the aromatic quality and stability of the bio-oil. Some of the principal challenges
fractions and decreases the methoxy, carboxylic and sugar frac- incurred in using pyrolytic biofuels as a substitute for petroleum
tions. Recycling of NCG increased the higher heating value and the oils, along with the potential solutions for each problem are
pH of the bio-oil as well as decreased the viscosity, oxygen content, described as under:
and density. More study is required for finding the optimum utili-
zation of the NCG. 11.1. Challenges with the feedstock
10. Energy perspective Although pyrolysis processes accept variable feed, the varying
nature of the feedstock leads to inconsistency in the product
The gross calorific values of the bio-oils obtained from pyrolysis behavior. The scale-up from the laboratory research to industrial
of lignocellulosic biomass are comparable to those of oxygenated pilot plants becomes difficult with this inconsistency. Methods of
fuels, such as methanol (23 MJ/kg) and ethanol (29.7 MJ/kg); while harvest and collection of biomass also alter the quality of the
the gross calorific values of bio-char are comparable to those of feedstock. Establishment of standards for feedstock quality can help
lignite (15e27 MJ/kg). These products of pyrolysis can be used for in avoiding this inconsistency to some extent. The standards can be
power generation [247]. However, the heating value of the bio-oil is in terms of acceptable moisture, in-homogeneity, dirt, and LHV.
highly dependent on the nature of feedstock, source, pre- Feed standardization is more important when the objective of
processing and reaction conditions. operation is to produce industrially important chemicals. Use of
Beis et al. [248] reported a calorific value of 41 MJ/kg for the bio- dedicated energy crops hybridized to improve the liquid yield and
oil (44% yield) obtained from the pyrolysis of safflower seeds. heating values is also an attractive solution.
€
Ozçimen and Karaosmanog lu [200] reported a calorific value of Ash content of the biomass is also a problem. The inorganics
36.4 MJ/kg of the bio-oil (59.7% yield) obtained from the pyrolysis present in the ash, especially potassium and calcium, catalyze
of rapeseed. Gang et al. [249] reported of bio-oil (31% yield) from biomass decomposition and char-forming reactions. Zhou et al. [257]
pyrolysis of waste bamboo at 500 C in a fluidized bed reactor, with reported a strong catalytic effect of potassium on co-pyrolytic ki-
a gross calorific value of 27.7 MJ/kg. Relatively less calorific values netics of wood biomass and low density polyethylene (WS/LDPE),
are observed in the pyrolysis of wood biomass. Solantausta et al. leading to decrease in peak decomposition temperature values.
[162] reported a heating value of 17.5 MJ/kg for the bio-oil (65e70% Meanwhile, an increase in char yield was found for all the potassium-
yield) obtained from pyrolysis of hardwood. The HHV values as treated WS/LDPE mixtures. The results from kinetic analysis showed
high as 21e30 MJ/kg for bio-char from corn cob have been reported an increasing trend for activation energy and pre-exponential factor
[193]. with increasing potassium concentration in the first stage of
The cost of production is an important factor that decides the decomposition, followed by a decreasing trend in the second stage.
fate of any process on the substantial scale. The studies on eco- Some of the char formed in these reactions eventually ends up in the
nomic analysis of bio-oil production, conducted in 80's and early bio-oil as suspended submicron particles. The presence of high
90's, by Scott and Piskorz [250], Beckman et al. [251], Cottam and concentrations of submicron char particles in bio-oil, can make it
Bridgwater [252], Freel et al. [253], and Solantausta et al. [162] gave challenging for combustion machinery, because of the potential
the cost of production of bio-oil higher than the cost of light fuel oil release of the ash and alkali metals during combustion [75].
at that time, by a factor of 1.09e2.7. Biomass prices have a strong Deashing of original biomass via treatment with mild acids has
influence on the economics of the process [247]. The cost of pro- been in literature for improving the bio-oil quality [259]. Deashing
duction is not only a function of feedstock, and process conditions, has also been demonstrated for increasing the rate of release of
but also dependent on the scale of operation. Solantausta et al. volatiles. Consequently, the residence time available for volatiles
[162] reported ~18% decrease in cost of bio-oil production when the inside the biomass particles decreases, also minimizing the sec-
plant capacity was increased by a factor of ~1.5. ondary reactions. This results in more higher-molecular-weight
The thermal efficiency of the system is a major factor in products available for condensation into bio-oil, giving higher
lowering the cost of operation. Using biochar and NHG for liquid yield with high heating value. However, the heating value is
providing heat of operation can significantly increase the thermal perceptibly decreased [260]. Raveendran et al. [42] studied the
efficiency of the process. Halouani and Farhat [254], demonstrated pyrolysis of twelve different biomass feedstock and observed that
a pilot plant of wood biomass carbonization coupled with a pro- the yield of pyrolysis vapors, devolatilization rate and the initial
vision for incineration of non-condensable smoke. The thermal decomposition temperature increased whereas the char yield
efficiency of the system increased from 42.33% to 89.51%, when decreased on demineralization of the biomass samples.
carbonization was performed using the heat of smoke incineration.
A method of bio-oil production, using the waste heat from blast 11.2. Complications in processing
furnace slag has also been demonstrated by Luo et al. [255].
Do and Lim [256] performed a techno-economic comparison of For efficient pyrolysis to take place, and especially for fast py-
three plant models: (1) Bioethanol and jet fuel production plant, (2) rolysis where high heating rates are required, heat transfer inside
Gasification plant for combined heat and power, and (3) Fast py- the biomass poses a challenge. Since biomass has a low thermal
rolysis and bio-oil upgrading plant. In their study, it was concluded conductivity, it needs to undergo size reduction or comminution
that fast pyrolysis and bio-oil upgrading are the most promising before feeding into the reactor. The power requirement for me-
plant model because of high economic potential. chanical comminution of biomass depends on the final particle size
and biomass characteristics [261]. Choi et al. [25] demonstrated a problems such as erosion and equipment blockage. Suspended char
decline in bio-oil yield from 55.7 to 47.9%, when feed particle size can also lead to slow rates of combustion, or occurrence of “spar-
was increased from 0.5 to 2.5 mm. klers” in combustion, leading to potential deposits or high carbon
Ablative reactors are exempted from such particle size monoxide emission. Char is also known to exhibit catalytic activity,
requirement. In these reactors, simultaneous pyrolysis reaction leading to potential cracking of bio-oil components and reduction
along with the simultaneous erosion of char layer takes place, thus of condensable yield up to 20% [146]. Hot vapor filtration can be
ensuring unhindered heat transfer. used to overcome this challenge. Increase in combustion rate, lower
Conventional heating methods using tube furnace or fluidized ignition delay, and low average molecular weight of the bio-oil has
bed reactor are widely used for pyrolysis of biomass; however, been demonstrated by removal of suspended char via hot vapor
these external heating methods consumed long heating duration filtration [266].
that results in low-quality products due to the secondary reactions. High viscosity of the biofuel can lead to high pressure drops in
Other disadvantages including more energy required for the heat- the pipelines leading to higher equipment cost and also the pos-
ing process, heat transfer resistance and heat losses to the sur- sibilities of leakage or even pipe rupture. High fuel viscosity leads to
rounding. Recently microwave pyrolysis was developed as an poor flow characteristics and combustion properties.
alternative heating source for pyrolysis process to overcome these Catalytic upgradation of bio-oil can help overcome most of these
problems. As a rapid pyrolysis process, microwave pyrolysis pre- challenges. Ghodke et al. [197] studied esterification of the bio-oil
vents the formation of secondary reaction thus improved the obtained from babul wood pyrolysis with 1-butanol using
quality of products produced. It also provides a uniform heating of Amberlyst-15, as a solid catalyst for increasing the stability. The ester
the sample due to volumetric heating of the materials [112]. In the formation significantly reduced the acidity and viscosity of the bio-
more recent works, pyrolysis assisted with solar heating was oil. The water released as byproduct of esterification was further
studied by Zeng et al. [262]. Integration of solar energy with py- removed by reactive distillation. However, catalysts deactivation by
rolysis is expected to lower the cost of operation. polymerization of furfural was identified as a key challenge. More
work on catalytic upgradation of bio-oils to improve its fuel char-
11.3. Product adversity acteristics have already been cited in section 7.4.
Integrated bio-oil and upgradation processes, with catalyst
Bio-oil from pyrolysis has a number of disadvantageous char- regeneration are attractive options. The Gas Technology Institute,
acteristics, which require consideration when intended to use the Birmingham, AL has developed and demonstrated at the pilot scale
oil as fuel. These characteristics prove to be undesirable in the based on the concept of integrated hydropyrolysis-
production, storage, transport, upgradation and utilization. hydroconversion (IH2®) a new catalytic technology for the direct
Moisture in bio-oil is also an undesirable fraction, as it lowers thermochemical conversion of woody biomass directly into
the heating value and flame temperature; it contributes to increase blendstocks, gasoline, and diesel fuels. In this concept, hydro-
in ignition delay and is also known to lowers the combustion rates pyrolysis is been carried out under high pressures of hydrogen
[199]. Presence of moisture in biofuel can lead to low calorific value (5e40 bar) and the vapors are in-situ hydrodeoxygenated to pro-
and in-homogeneity in the liquid. In-homogeneity in biofuel leads duce fuels [267].
to layering or partial separation of phases, and filtration problems.
Because of the reactivity of the oxygenated functional groups, the 12. Conclusions
bio-oil has thermal instability and storage difficulties [263].
Polymerization or deterioration of the liquid can take place at Pyrolysis of lignocellulosic biomass has a potential to provide
temperatures around 100 C, which can adversely affect physical environmental friendly future fuels/chemicals. The potential of bio-
properties of the bio-oil such as viscosity, phase separation, and oil is increasingly being acknowledged, leading to identification of
carbonaceous deposition. Solid coke like products may form as the several ideal lignocellulosic species as feedstock for pyrolysis,
result of these polymerization reactions, during distillation of the including wood biomass, agricultural residues, and dedicated en-
oil. Condensation reactions such as etherification and esterification ergy crops. Various reactor configurations have also been studied
may taking place during the storage of bio-oil, not only lead to the and are being modified to implement high efficiency. However,
formation of heavier compounds, but also increase the already presence of moisture in the biomass, uneven distribution, and
undesirable moisture content [206]. varying nature of the feedstock, lead to production of bio-oil which
Low pH values attributed to the presence of organic acid com- is inferior in quality in comparison with the conventional fossil
pounds (e.g. acetic and formic acids) in the bio-oil can cause fuels. Presence of oxygen, acidic compounds, and instability in the
corrosion of the vessel and the pipework. These oils are corrosive to bio-oil are some of the other major concerns in establishment of
conventional building materials such as carbon steel and pyrolysis on substantial scale. Research in the field of bio-oil
aluminum. Use of Polyolefins as the construction material, where upgradation, production of high energy feedstock, and process
other circumstances permit has been recommended in the litera- intensification as a bio-refinery to lower the cost of production can
ture [264]. Bridgwater concluded mild steel as not suitable for help in overcoming these challenges. The successful and sustain-
handling or storage of such fuel, and suggested polypropylene able utilization of pyrolytic oils for substituting the fossil fuels will
piping to overcome problem [265]. depend on development of integral bio-refineries having a supply
Ash is an undesirable component of the bio-oil, which can lead of quality feedstock, cheap and easy-to-regenerate catalysts for bio-
to erosion, corrosion and kicking problems in the engines and oil upgradation, reactors with high thermal efficiencies, and
valves. The ash problem becomes more important when the ash adapting energy market.
content of the fuel is higher than 0.1%. Sodium, potassium and
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Renewable Energy 129 (2018) 695e716

Contents lists available at ScienceDirect

A comprehensive review on the pyrolysis of lignocellulosic biomass

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

cellulose has a hydrolysis-resistant crystalline structure, hemi- 3.1. Wood biomass

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

Wood based biomass

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

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

three main components, with the extent of convolution depend-

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

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

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

shows typical DSC curves for individual biomass components. The

thermal decomposition peaks are endothermic for volatilization

position pattern of hemicellulose and lignin can be attributed to

decomposition of cellulose taking place by full volatilization.

4.6. Kinetic analysis

Kinetic study of biomass pyrolysis is essential to understand

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

rameters. The knowledge of kinetic parameters, activation energy,

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

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

mixtures, where nature of reaction changes with reaction pro-

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

mination of activation energy. These methods are based on the

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

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

differential and integral methods fall under the category of iso-

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

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

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

Pyrolysis is the term given to the thermal depolymerization of

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

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

for pyrolysis of several agricultural and wood-based biomass in

inert atmosphere results in the production of organic vapor

composed of fragments of cellulose, hemicellulose, and lignin

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

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

The non-condensable gases leave the reaction system and can

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

The product distribution of the bio-oil predominantly depends

decomposition of lignin took place in a wide range of temperature

releasing behaviors of H2 and the total gas yield were measured

the dehydration and breakdown of sugar molecules result in the

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

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

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

between these components that determine the product distribu-

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

bonds inﬂuence the pyrolytic behavior of biomass and may cause

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

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

interactions between components may differ in a physical mixture

from an actual biomass sample as the structure of biomass will

The conditions for pyrolysis process, viz. temperature, heating

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

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