Review

Biomass pyrolysis: a state-of-

the-art review
B. V. Babu, Birla Institute of Technology and Science, Pilani, India

Received February 20, 2008; revised version received June 1, 2008; accepted June 19, 2008
Published online August 4, 2008 in Wiley InterScience (www.interscience.wiley.com); DOI: 10.1002/bbb.92;
Biofuels, Bioprod. Bioref. 2:393–414 (2008)

Abstract: Biomass pyrolysis is a process by which a biomass feedstock is thermally degraded in the absence of
air/oxygen. It is used for the production of solid (charcoal), liquid (tar and other organics) and gaseous products.
These products are of interest as they are possible alternate sources of energy. The study of pyrolysis is gaining
increasing importance, as it is not only an independent process, it is also a first step in the gasification or com-
bustion process, and has many advantages over other renewable and conventional energy sources. Studies have
been conducted on pyrolysis of biomass and other substances by several researchers. The actual reaction scheme
of pyrolysis of biomass is extremely complex because of the formation of over a hundred intermediate products.
Modeling of pyrolysis includes chemical kinetics model, heat transfer model and mass transfer model. Various
kinetic models, heat and mass transfer models reported in the literature and our previous study are reported in the
present review with experimental validations to provide the current status of the study. Plasma pyrolysis provides
high temperature and high energy for reaction as the reaction sample is rapidly heated up to a high temperature.
This review also covers the experimental and modeling study status of plasma-assisted pyrolysis. © 2008 Society
of Chemical Industry and John Wiley & Sons, Ltd

Keywords: pyrolysis; renewable energy; biomass; gasification; modeling; heat transfer; mass transfer; kinetics;
plasma pyrolysis

Introduction are finite and those that are, on any human scale, effectively
perpetual or everlasting. The finite resources comprise a
nergy around us can be stored, converted and ampli- number of organically based substances – coal, crude oil, oil

E fied in many different ways. Energy resources may be

categorized as either finite (e.g. minerals) or perpetual,
such as the so-called renewable resources (solar, wind, tidal,
etc.). In the case of finite resources, reserves denote the
amount within the designated resource that is recoverable
under specified criteria. Whilst each major energy source has
its own characteristics, applications, advantages and disad-
vantages, the fundamental distinction is between those that
shale, natural bitumen and extra-heavy oil, and natural gas,
together with the metallic elements uranium and thorium.
The principal perpetual resources are solar energy, wind power
and bioenergy, all of which are ultimately dependent on an
extra-terrestrial source, namely the sun. Other perpetual
resources are various forms of marine energy – tidal energy,
wave power and ocean thermal energy conversion (OTEC).
There are also two types of energy resource – peat and

Correspondence to: B. V. Babu, Professor of Chemical Engineering & Dean, Educational Hardware Division, Birla Institute of Technology

and Science (BITS) PILANI – 333 031 (Rajasthan) India. E-mail: bvbabu@bits-pilani.ac.in; profbvbabu@gmail.com

© 2008 Society of Chemical Industry and John Wiley & Sons, Ltd 393
BV Babu
geothermal energy – which are to some extent intermediate
in nature, with both finite and perpetual elements in their
make-up. Bioenergy is arguably the one truly renewable
energy resource, in that each new crop or harvest represents
a partial renewal of its resource base, which is itself subject to
constant depletion through its use as a fuel or feedstock. The
other perpetual energy resources are available on a contin-
uing, albeit varying, basis, are not depleted by the utiliza-
tion of their energy content, and are therefore not subject to
renewal.1 Table 1 shows the comparison of various energy
sources in terms of advantages, disadvantages and their
natural reserves. Information related to the natural reserves
given in Table 1 is collected from the executive summary of
the committee of survey of energy sources.1
The world primary energy consumption is about 400 EJ/
year, mostly provided by fossil fuels (80%). The effects on
global and environmental air quality of pollutants released
into the atmosphere from fossil fuels provide strong argu-
ments for the development of renewable energy resources.
Clean, domestic, renewable energy is commonly accepted as
the key for future life. The renewables collectively provide
14% of the primary energy, in the form of traditional
biomass (10%), large (>10 MW) hydropower stations (2%),
and the ‘new renewables’ (2%). Nuclear energy provides
6%. The World Energy Council expects the world primary
energy consumption to have grown by 50–275% in 2050,
depending on different scenarios. The renewable energy
sources are expected to provide 20–40% of the primary
energy in 2050 and 30–80% in 2100. The technical poten-
tial of the renewables is estimated at 7600 EJ/year, and thus
certainly sufficiently large to meet future world energy
requirements. Of the total electricity production from
renewables of 2826 TWh in 1998, 92% came from hydro-
power, 5.5% from biomass, 1.6% from geothermal and 0.6%
from wind. Solar electricity contributed 0.05% and tidal
0.02%. The electricity cost is 2–10 USc⁄/kWh for geothermal
and hydro, 5–13 USc⁄/kWh for wind, 5–15 USc⁄/kWh for
biomass, 25–125 USc⁄/kWh for solar photovoltaic and 12–18
US¢/kWh for solar thermal electricity. Biomass constitutes
93% of the total direct heat production from renewables,
geothermal 5%, and solar heating 2%. Heat production from
renewables is commercially competitive with conventional
energy sources. Direct heat from biomass costs 1–5 USc⁄/kWh,
394 © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
Review: Biomass pyrolysis
while that from geothermal costs 0.5–5 USc⁄/kWh, and from
solar heating it costs 3–20 USc⁄/kWh.2
Biomass is the term used to describe all biologically
produced matter and it is the name given to all Earth’s
living matter. It is a general term for material derived from
growing plants or from animal manure (which is effectively
a processed form of plant material). Solar energy drives the
photosynthesis process in all the plant matter. The chemical
energy contained in the biomass is derived from solar energy
using the process of photosynthesis. (Photo means to do with
light and synthesis is the putting together.) This is the process
by which plants take in carbon dioxide and water from their
surroundings and, using energy from sunlight, convert them
into sugars, starches, cellulose, lignin etc., which make up
vegetable matter, loosely termed carbohydrates (and shown
for simplicity as [CH2O]). Oxygen is produced and emitted.
CO2 + 2H2O → [CH2O] + H2O + O2 (1)
Biomass energy is derived from plant and animal material,
such as wood from natural forests, waste from agricultural
and forestry processes, and industrial, human or animal
wastes. The stored energy in the plants and animals (that
eat the plants and other animals), or the waste that they
produce is called biomass energy. It is a natural process that
all biomass ultimately decomposes to its molecules with the
release of heat. And the combustion of biomass imitates the
natural process. So the energy obtained from biomass is a
form of renewable energy and it does not add carbon dioxide
to the environment in contrast to the fossil fuels.3 Of all the
renewable energy sources, biomass is unique in that it is,
effectively, stored solar energy. Furthermore, it is the only
renewable energy source of carbon and is able to convert
into convenient solid, liquid and gaseous fuels.4
Bioenergy is essentially renewable or carbon neutral.
Carbon dioxide released during the energy conversion
of biomass (such as combustion, gasification, pyrolysis,
anaerobic digestion or fermentation) circulates through the
biosphere, and is reabsorbed in equivalent stores of biomass
through photosynthesis. Figure 1 shows the combustion of
wood and thereby CO2 generation. It also depicts that net
CO2 generation is zero as new biomass is developed photosyn-
thetically. Biomass for energy is a unique form of renewable,
solar energy. Of the massive 178,000 × 1012 Watts of solar
Review: Biomass pyrolysis
Table 1. Comparison of energy sources.
Energy
source Main features
Coal • Finite energy source
• The most rapidly growing fuel on a
global basis
Oil • Finite energy source.
• Several different categories of oil,
each having different costs, char-
acteristics and, above all, depletion
profiles.
• In terms of global consumption,
crude oil remains the most important
primary fuel, accounting for 36.4% of
the world’s primary energy consump-
tion (without biomass).
Nuclear Power • Generated using uranium, which is
a metal mined in various parts of the
world.
• Nuclear fission of Uranium produces
heat.
• Neutrons smash into the nucleus
of the uranium atoms, which split
roughly in half and release energy in
the form of heat.
• No smoke or carbon dioxide produc-
tion.
• Huge amounts of energy from small
amounts of fuel with small amounts
of waste.
Geothermal • The natural heat of the Earth.
Energy
Hydro-electric • Currently the largest of the
perpetual or so-called renewable
energy resources.
Solar Energy • The Sun is the most abundant
permanent source of energy.
• The annual solar radiation reach-
ing the earth is over 7500 times
the world’s annual primary energy
consumption of 450 exajoules.
Wind Energy • Winds are generated by complex
mechanisms involving the rotation of
the earth, heat energy from the sun,
the cooling effects of the oceans and
polar ice caps, temperature gradi-
ents between land and sea and the
physical effects of mountains and
other obstacles.
© 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
Disadvantages
• Burning of fossil fuel produces
dust, smoke and oxides of impuri-
ties, which may lead to environ-
mental pollution.
• Burning any fossil fuel produces
carbon dioxide, which contributes
to the ‘greenhouse effect’, warming
the Earth.
• Burning fossil fuels also produces
photochemical pollution from
nitrous oxides, and acid rain from
sulfur dioxide.
• Waste produced is highly
dangerous.
• Waste must be sealed up and
buried for many years to allow the
radioactivity to die away.
• Lot of investment on safety – if it
does go wrong, a nuclear accident
can be a major disaster.
– • Not a clear-cut example of a
– • Total world hydro capacity to
• Large investment cost for solar
photovoltaic collectors.
• Large investment cost for
windmills.
BV Babu
Reserves
• 850 billion tonnes of coal as
currently recoverable.
• Available in more than 70
countries worldwide.
• Expected resources of 82 billion
tones.
• 47% of the total reserves of
conventional oil discovered so far
have been consumed.
• Cumulative crude oil production
until the end of 2005 reached
143 billion tonnes – half of it was
produced within the last 23 years.
• Not renewable; once all the
Earth’s uranium dugged up and
used it, there is not any more.
perpetual source of energy as is
solar, wind and marine energy.
nearly 778 GW.
–
• Some of the windiest regions are
to be found in the coastal regions
of the Americas, Europe, Asia and
Australasia.
• The world’s wind resources are
vast: it has been estimated that
if only 1% of the land area were
utilized, and allowance made for
wind’s relatively low capacity fac-
tor, wind-power potential would
roughly equate to the current level
of worldwide generating capacity.
395
BV Babu
Figure 1. Lifecycle of forest biomass (Source: http://www.paisatge.
net/SapreRenovables/ENG/eSproj.htm).
energy that falls on the Earth’s surface, some 0.02% or
40 × 1012 Watts is captured by plants via photosynthesis and
bound into biomass energy. This translates into the produc-
tion of some 220 billion ‘dry’ tonnes of biomass per year
which, as an energy source, represents some ten times the
world’s total current energy use. Currently some 15% of the
planet’s energy requirements are met from biomass, mainly
for cooking and heating in developing countries, but also
increasingly for fuelling a growing number of large-scale,
modern biomass energy plants in industrialized countries.
By comparison, the world population consumes around
10EJ/year of energy in the form of food, which of course is a
biomass energy resource in itself.5
Conventionally biomass was used in a similar way to fossil
fuels, by burning it at a constant rate in boiler furnace to
heat water and produce steam. Biomass-generated steam
passes through the multiple blades of a turbine, spinning
the shaft. The turbine shaft drives an electricity generator
which produces an alternating current for local use or to
supply the national grid. Wood is still a predominant fuel in
many non-OPEC, tropical, developing countries and it will
continue to be used for many years. It competes well with
396 © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
Review: Biomass pyrolysis
fossil fuels, because it is renewable, and with soft energies,
like solar and wind, on account of its energy-storage capa-
bility. It is being used in the domestic (for cooking and water
heating), commercial (water heating), and industrial (for
water heating and process heat) sectors and also in rural
industries, like brick kilns, potteries etc.6
In nature, biomass is not concentrated, and so, the use of
naturally occurring biomass requires transportation, which
increases the cost and reduces the net energy production.
Biomass is having a low bulk density, which makes trans-
portation and handling more difficult and costly. Apart
from transportation, incomplete combustion of biomass
generates a concern among the environmentalists, as it may
produce organic particulate matter, carbon monoxide and
other organic gases. If high-temperature combustion is used,
oxides of nitrogen would be produced. The health impact
of air pollution is a significant problem in developing coun-
tries, where fuel wood is burnt inefficiently in open fires for
domestic cooking and space heating.4
The conversion technologies for utilizing biomass can
be separated into four basic categories: direct-combustion
processes, thermochemical processes, biochemical proc-
esses and agrochemical processes. The evaluation of the
potential of thermochemical biomass conversion for produc-
tion of power and energy requires extensive and quantita-
tive analysis of the thermal and chemical behavior of the
different classes of feedstocks as operating conditions are
varied.7 Conversion characteristics can be grouped into
thermochemical (ash and volatile yields, reactivity of volatile
products etc.), intra-particle rate (thermal properties, mois-
ture content, size, kinetics and energetics of chemical proc-
esses etc.) and extra-particle rate (heat transfer from reactor
to particle, residence time and mass transfer conditions,
dependent in turn on the type of conversion unit).8 There is
a further classification of intra-particle rate characteristics
into two main categories, that is, those related to feedstock
preparation, such as particle size and moisture content, and
the intrinsic physical and chemical properties. In relation to
the devolatilization (pyrolysis) stage, the effects of particle
size have been extensively examined by both experiment and
comprehensive theories.9,10
Physicochemical properties of biomass depend widely on
the type of feedstock. For example, density may vary from
Review: Biomass pyrolysis
100 kg/m3 (balsa, bagasse and straw) to 1200 kg/m3 (lignum
vitae).11 It is expected that effective physical properties of
char should reflect those of virgin biomass and, thus, show
significant variation with the feedstock.
There has been an increasing interest for thermochemical
conversion of biomass and urban wastes for upgrading the
energy in terms of more easily handled fuels, namely gases,
liquids, and charcoal, in the past decade. The thermochem-
ical conversion of biomass (pyrolysis, gasification, combus-
tion) is one of the promising routes amongst the renewable
energy options of future energy. It is a renewable form with
many ecological advantages. Thermochemical conversion
processes can be subdivided into gasification, pyrolysis, and
direct liquefaction. Gasification is a process of conversion
of solid carbonaceous fuel into combustible gas by partial
combustion. The resulting gas, known as producer gas, is a
mixture of carbon monoxide, hydrogen, methane, carbon
dioxide and nitrogen. The producer gas is more versatile
than the original solid biomass. It is burnt to produce
process heat and steam or used in gas turbines to produce
electricity.12 In pyrolysis and liquefaction both, feedstock
organic compounds are converted into liquid products. In
case of liquefaction, feedstock macromolecules compounds
are decomposed into fragments of light molecules in the
presence of a suitable catalyst. These unstable and highly
reactive fragments repolymerize into oily compounds
having appropriate molecular weights, whereas in pyrolysis,
catalysts are not used and light decomposed fragments are
converted to oily compounds through homogeneous reac-
tions in the gas phase. The difference in operating conditions
for liquefaction and pyrolysis are shown in Table 2.4
There is a tremendous potential for obtaining renewable
energy from biomass and other forms of biowastes. Pyrolysis
(conventional and plasma-based) is the route through which
useful energy can be obtained from waste. Th is review is
a pointer in this direction for focused research in the near
future. The overall objectives of this review are: (i) to provide
Table 2. Comparison of liquefaction and pyrolysis.
Process Temperature
Liquefaction 525–600
Pyrolysis 650–800
© 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
BV Babu
the chronological development in the field of experimental
and theoretical (mathematical modeling and simulation)
aspects associated with pyrolysis; and (ii) to bring out clearly
the present status of the research in the field of conven-
tional and plasma pyrolysis of various biomasses and the
existing research gaps, emphasizing the scope and potential.
The main areas covered in this review include: pyrolysis,
chemical kinetic modeling, heat mass and momentum
transfer modeling, simulation of model equations,
experimental validation, and plasma-assisted pyrolysis.
Pyrolysis
The pyrolysis of biomass is a promising route for the produc-
tion of solid (charcoal), liquid (tar and other organics, such
as acetic acid, acetone and methanol) and gaseous products
(H2 , CO2 , CO). These products are of interest as they are
possible alternate sources of energy. Pyrolysis is a process
by which a biomass feedstock is thermally degraded in the
absence of oxygen/air. The study of pyrolysis is gaining
increasing importance, as it is not only an independent
process, but it is also a fi rst step in the gasification or
combustion process.13,14 The basic phenomena that take
place during pyrolysis are: (i) heat transfer from a heat
source, leading to an increase in temperature inside the fuel;
(ii) initiation of pyrolysis reactions due to this increased
temperature, leading to the release of volatiles and the
formation of char; (iii) outflow of volatiles, resulting in
heat transfer between the hot volatiles and cooler unpyro-
lysed fuel; (iv) condensation of some of the volatiles in the
cooler parts of the fuel to produce tar; and (v) autocatalytic
secondary pyrolysis reactions due to these interactions.7,5–17
Pyrolysis can be used as an independent process for the
production of useful energy (fuels) and/or chemicals. Most
biomass materials are chemically and physically heteroge-
neous, and their components have different reactivities and
yield different products. The overall process of pyrolysis
can be classified into primary and secondary stages. When
Pressure (MPa) Drying
5–20 Unnecessary
0.1–0.5 Necessary
397
BV Babu
a solid particle of biomass is heated in an inert atmosphere
the following phenomena occur. Heat is first transferred
to the particle surface by radiation and/or convection and
then to the inside of the particle. The temperature inside
the particle increases, causing (i) removal of moisture
that is present in the biomass particle; and (ii) the pre-
pyrolysis and main pyrolysis reaction takes place. The heat
changes due to the chemical reactions, and phase changes
contribute to a temperature gradient as a function of time,
which is nonlinear. Volatiles and gaseous products flow
through the pores of the particle and participate in the heat-
transfer process. The pyrolysis reactions proceed with a rate
depending upon the local temperature. During the pyrolysis
process, the pores of the solid are enlarged, and the solid
particle merely becomes more porous because the biomass
converts into gases as discussed by Curtis and Miller.18
According to Anthony and Howard,19 the enlarged pores of
the pyrolyzing solid offer many reaction sites to the volatile
and gaseous products of pyrolysis and favor their interac-
tion with the hot solid. Inside the pyrolyzing particle, heat
is transmitted by the following mechanisms: (i) conduction
inside the solid particle; (ii) convection inside the particle
pores; and (iii) convection and radiation from the surface of
the pellet.
Depending upon the operating conditions, the pyrolysis
process can be divided into three subclasses: conventional
pyrolysis (carbonization), fast pyrolysis, and flash pyrolysis.
The ranges of the main operating parameters for pyrolysis
processes are given in Table 3. Conventional pyrolysis is
defined as the pyrolysis that occurs under a slow heating
rate. This condition permits the production of solid, liquid,
and gaseous pyrolysis products in significant portions. The
first stage of biomass decomposition occurs between 395
and 475 K and is called as pre-pyrolysis. During this stage,
some internal rearrangement, such as water elimination,
bond breakage, appearance of free radicals, and formation of
Table 3. Range of main operating parameters for pyrolysis processes.
Parameters Conventional pyrolysis
Pyrolysis temperature (K) 550–950
Heating rate (K/s) 0.1–1.0
Particle size (mm) 5–50
Solid residence time (s) 450–550
398 © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
Review: Biomass pyrolysis
carbonyl, carboxyl, and hydroperoxide groups, takes place.20
The second stage of the solid decomposition corresponds
to the main pyrolysis process. It proceeds with a high rate
and leads to the formation of the pyrolysis products. During
the third stage, the char decomposes at a very slow rate and
carbon-rich residual solid forms. If the aim is the production
of mainly liquid and/or gaseous products, a fast pyrolysis
is recommended. The achievement of fast heating rates
requires high operating temperatures, very short contact
times, and very fi ne particles. Flash pyrolysis differs strongly
from that of conventional pyrolysis performed slowly with
massive pieces of wood. Flash pyrolysis gives mostly gaseous
products due to the high heating rate and very small particle
size.21 Hydropyrolysis (pyrolysis in a hydrogen atmosphere)
is also considered to have a potential application in the
conversion of biomass to liquids enriched in hydrocarbons.22
Biomass is mainly composed of three constituents which
are hemicelluloses, cellulose, and lignin. There are minor
amounts of extractives also present. Each component
of biomass pyrolyzes at different rates and by different
mechanisms and pathways. It is believed that as the reac-
tion progresses, the carbon becomes less reactive and forms
stable chemical structures, and consequently the activation
energy increases as the conversion level of biomass increases.
Cellulose and hemicellulose decomposes over a very narrow
temperature range as compared to lignin. The rate and
extent of degradation of each of these components depends
on the process parameters of reactor type, temperature, and
particle size heating rates and pressure.23 Thermal degrada-
tion properties of hemicelluloses, cellulose, and lignin can
be summarized as follows:
Thermal degradation of hemicelluloses > of cellulose > of
lignin. The hemicelluloses break down first, at temperatures
of 470 to 530 K, and cellulose follows in the temperature
range 510 to 620 K, with lignin being the last component to
pyrolyze at temperatures of 550 to 770 K.24
Fast pyrolysis Flash pyrolysis
850–1250 1050–1300
10–200 < 1000
<1 < 0.2
0.5–10 < 0.5
Review: Biomass pyrolysis BV Babu

Kinetics of pyrolysis
Degradation kinetics of lignocellulosic fuels was studied in
either dynamic or static conditions. Static conditions are
achieved by maintaining the selected constant temperatures
in the pyrolyzing chamber. During dynamic conditions,
biomass particles submitted in pyrolyzing chamber experi-
ence an increase in temperature with time according to an
assigned heating rate. Heating rates highly affect the reaction
process. Limitations are encountered in both techniques.
It is difficult to maintain higher heating rates in laboratory
conditions, those usually achieved in gasification or pyrolysis
reactors. On the other hand, in the static analysis, tests are
carried out according to two different methodologies to
attain the isothermal stage. In the first methodology, the
small dynamic stage consists of very slow heating rates to
avoid spatial gradients of temperature. In the second meth-
odology, very fast, external, heat-transfer rates to keep short
the first dynamic stage are used. However, in the first case,
the weight loss is not negligible during heating and the subse-
quent interpretation of the data may be lacking an important
part of the whole process. In the second case, the results may
be seriously affected by heat transfer limitations; unless an
accurate control of the sample temperature is accomplished.
Different classes of mechanisms were proposed for the
pyrolysis of wood and other cellulosic materials.25,26 The
models are classified into three categories: one-step global
models; one-stage multireaction models; and two-stage
semiglobal models. The first category of models considers
pyrolysis as a single-step first order reaction.
Parallel reactions:
Virgin biomass (Volatiles + Gases)1 (2)
Virgin biomass (Char)1 (3)
As shown in Table 4, pyrolysis process is described by
means of a one-step global reaction for degradation or
devolatilization by many research groups.27–33 Thurner and
Mann27 conducted experiments on oak wood of 650 μm in

Table 4. Single-step mechanisms for isothermal pyrolysis of wood.27–33

Feedstock
(variety, size Experimental Reaction Kinetic constants
Reference and mass) system Tr (K) mechanism E (kJ/mol), A(s−1)
Thurner and Oak, 650 µm Tube furnace 573–673 dY ⎛ 106.5 ⎞
= − kY k = 2.47 × 106 exp ⎜ −
Mann (1981) dt ⎝ RT ⎟⎠

Gorton and Hardwood Entrained flow 677–822 dY ⎛ 89.52 ⎞

= − kY k = 1.483 × 106 exp ⎜ −
Night (1984)
300–350 µm
reactor dt ⎝ RT ⎟⎠

Ward and Wild cherry Tube furnace 538–539 dY ⎛ 173.7 ⎞

= − kV (Y − YC∞) kV = 11.9 × 1011 exp ⎜ −
Braslaw (1985) dt ⎝ RT ⎟⎠
YC∞ = 0.25 − 0.3

Wagenear et al. Pine 100 m–125 TGA 553–673 dY ⎛ 150 ⎞

= − kY k = 1.4 × 1010 exp ⎜ −
(1994) µm
Drop tube 773–873 dt ⎝ RT ⎟⎠

Di Blasi and Beech < 80 µm, 9 g Tube furnace 573–708 dY ⎛ 141⎞

= − kY k = 3.6 × 108 exp ⎜ −
Branca (2001) dt ⎝ RT ⎟⎠

Samolada and Fir wood Batch fluid-bed 673–773 dYV ⎛ 56.48 ⎞

= − kV (YV∞ − YV ) kV = 1.36 × 102 exp ⎜ −
Vasalos (1991)
300–425 µm, 2 g
reactor dt ⎝ RT ⎟⎠
YV∞ = 0.557

Reina et al. Forest waste, TGA 498–598 dY ⎛ 124.87 ⎞

(1998) <1000 µm, 25 mg = − kV (Y − YC∞) kV = 7.68 × 107 exp ⎜ − ⎟
dt ⎝ RT ⎠
YC∞ ≅ 0.25

973–1173 dY ⎛ 91.53 ⎞
= − kV (Y − YC∞) kV = 6.33 × 102 exp ⎜ −
dt ⎝ RT ⎟⎠
YC∞ ≤ 0.15

© 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb 399
BV Babu Review: Biomass pyrolysis

Table 5. Multistep mechanisms for isothermal pyrolysis of wood.36–37

Feedstock
(variety, size Experimental Reaction Kinetic constants
Reference and mass) system Tr (K) mechanism E (kJ/mol), A(s−1)
Barooah and Beech, 400–700 µm, Batch fluid-bed 523–673 dY T < 603 K
Long (1976) 40 g reactor = − kIY
dt
⎛ 18 ⎞
k I = 5.3 × 10−2 exp ⎜ −
n
⎝ RT ⎟⎠
dY ⎛ Y − YC∞⎞
= − k II ⎜
dt ⎝ 1− YC∞ ⎟⎠ ⎛ 17 ⎞
k II = 10.67 exp ⎜ −
⎝ RT ⎟⎠
,
YC∞ = 0.48 − 0.8 n=2

T > 603 K

⎛ 84 ⎞
k I = 2.33 × 104 exp ⎜ −
⎝ RT ⎠⎟

⎛ 115 ⎞
k II = 4 × 109 exp ⎜ −
⎝ RT ⎟⎠
,
n=2

Alves and Pine, 180–220 µm, TGA 525–860 k

YV 1∞ = 0.19, SV 1 ⎯⎯⎯
V1
→G kV 1 = 7 × 104 exp ( −83 RT )
Figueredo 10 mg
(1988)
k
YV 2∞ = 0.5, SV 2 ⎯⎯⎯
V2
→G kV 2 = 2 × 109 exp ( −146 RT )

YV 3∞ = 0.02, SV 3 ⎯⎯⎯
V3 k
→G kV 3 = 4.3 × 103 exp ( −77 RT )

YV 4∞ = 0.03, SV 4 ⎯⎯⎯
V4 k
→G kV 4 = 2.9 × 10 exp ( −146 RT )

YV 5∞ = 0.02, SV 5 ⎯⎯⎯
V5 k
→G kV 5 = 5.1 × 106 exp ( −139 RT )

YV 6∞ = 0.02, SV 6 ⎯⎯⎯
V6 k
→G kV 6 = 3.2 × 105 exp ( −130 RT )

tube furnace reactor for the temperature range of 573–673 K.
Gorton and Night28 performed experiments on hardwood of
the size 300–350 μm in entrained flow reactor for the temper-
ature range of 677–822 K. Ward and Braslaw,29 Wagener
et al.30 Di Blasi and Branca,31 Samolada and Vasalos,32 and
Reina et al.33 performed thermal degradation studies on
various biomasses and of size less than 1 mm. The value of
activation energy is least (56.48 kJ/mol) for fir wood reported
by Samolada and Vasalos32 and maximum for wild cherry
(173.7 kJ/mol) reported by Ward and Braslaw.29
Secondary interactions:
(Volatiles + Gases)1 + (Char)1 (Volatiles + Gases)2
+ (Char)2
The second category of models discuss those mechanisms,
which consider simultaneous and competing first order
reactions in which virgin wood decomposes into different
constitutes of pyrolysis products, namely, tar, char, and gases
(Reactions (2) & (3)). The third class of models considers
pyrolysis to be a two-stage reaction, in which the products of
the first stage break up further in the presence of each other
to produce secondary pyrolysis products. Such models are
presented for wood by Koufopanos et al.34,35 (Reactions (2),
(3) & (4)). Koufopanos et al.34,35 carried out isothermal mass
change determination of beech wood, olive husks, hazelnut
shells and corn cobs to obtain the kinetic data for the
proposed scheme. It is shown that the rate of pyrolysis of one
biomass type could be represented by the sum of the corre-
sponding rates of the main biomass components (cellulose,
hemicellulose and lignin). It is also reported that pyrolysis
(4)
of lingocellulosic materials of size less than 1 mm is kineti-
cally controlled and, for larger particles, kinetic equations
are required to be coupled with equations describing the
transport phenomena.34,35 Barooah and Long36 performed

400 © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
Review: Biomass pyrolysis
the pyrolysis of beech wood in a batch fluid-bed reactor for a
particle size of 400–700 μm (Table 5). A kinetic model based
on a two-stage process in the temperature range 523–673 K is
proposed and validated. Two sets of kinetic parameters
(activation energies of 17–115 kJ mol−1) are needed,
depending on a limit temperature of 603 K.36 Alves and
Figueredo37 conducted TGA experiments on pinewood of
size 220 μm covering the temperature range of 525–860
K. Six parallel reactions corresponding to different volatile
fractions are proposed by Alves and Figueredo.37 The first
two, quantitatively more important, were associated with
hemicellulose and cellulose, respectively (activation energies
of 83 and 146 kJ mol−1). The other components were assumed
to correspond mainly to parts of the lignin macromolecule
(activation energies between 60 and 130 kJ mol−1). The
highly different reaction mechanisms and kinetic constants
proposed indicate that further analysis is needed about the
multistep degradation kinetics of wood under isothermal
conditions.
The scheme of reactions of Koufopanos’ models is adapted
by Jalan and Srivastava 38–40 and Babu and Chaurasia.13
Chan41 proposed a mechanism where volatiles and tar
formed by primary pyrolysis undergo secondary pyrolysis.
The other primary reactions of formation of char and gas
from wood are parallel and competing with the tar forma-
tion reaction. Babu and Chaurasia7,12–17 did extensive
modeling and simulation on pyrolysis. The kinetic scheme
proposed by Koufopanos et al.34 for the pyrolysis of biomass
based on the two-stage model is accepted and validated.
The model proposed by Babu and Chaurasia15 includes
kinetic and heat-transfer effects for the shrinking biomass
particle. Th is model was again improved to incorporate
simultaneous effects of kinetics and transport of heat, mass
and momentum.16 Di Blasi42 proposed a mathematical
model, which includes transport phenomena and chemical
reactions for the pyrolysis of thermoplastic polymers
(polyethylene). It was found that depolymerization and
melting are followed by devolatilization. Surface regres-
sion, property variation, heat convection and conduction
were considered in the proposed model. Simulations were
carried out for external heating conditions corresponding
to fi xed-bed reactors, hot-plate contact and fi re-level
radiation exposures.
© 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
BV Babu
Chao-Hsiung et al.43 performed the thermogravimetric
studies of paper mixtures in municipal solid waste (MSW).
The pyrolysis kinetics of a mixture of the four principal
papers (uncoated and coated printing/writing papers,
newsprint, and tissue paper) in MSW was investigated.
The experiments were carried out in a nitrogen environ-
ment over the temperature range of 450 to 900 K at various
constant heating rates of 1, 2, and 5 Kmin–1. The pyrolysis
of a paper mixture is described by a two reaction model as
described below:
Papers Intermediates + Volatiles (5)
Intermediates Solid residues + Volatiles (6)
The experimental results were satisfactorily fitted by the
proposed chemical reaction kinetic equations.
Balci et al.44 performed the thermogravimetric experiments
for the hazelnut shell and other lignocellulosic biomasses,
and proposed several kinetic models. In these kinetic models,
an exponential decrease of solid reactivity with respect to
conversion level is proposed and the rate expression based
on first-order decomposition of the reactive solid is defined
in terms of fractional conversion. Arrhenius relation of rate
constant is replaced with an expression, where rate constant
is expressed as a function of extent of reaction. Demirbas45
performed the thermogravimetric experimental runs and
presented the weight-loss data for different particle sizes
of ground hazelnut shell and for various heating rates.
An experimental technique comprising a simplified, fast
pyrolysis device for obtaining the pyrolysis products and
kinetic parameters is presented. The effects of heating rate,
particle size, reaction temperature and catalyst are studied
by performing the experiments. Kinetic analysis has also
been carried out but the expression for the kinetic constants
with respect to temperature is not developed, and the experi-
mental data validation with theoretical models for these
experiments are not reported in the literature. Experimental
and modeling studies have been conducted on pyrolysis
by many researchers.7,12–17,21,34,35,46–49 Kinetic modeling
of lignocellulosic biomass by method of least squares is
performed by Varhegyi et al.49 by using thermogravimetry
data. Experiments are performed on large wood particles
and a mathematical model is presented for the packed-bed
pyrolysis.50 Thermogravimetric data has been generated to
study the kinetics of isothermal degradation of wood.51
401
BV Babu Review: Biomass pyrolysis

The kinetic model developed by Balci et al.44 is modified
and used for the hazelnut-shell biomass of 0.180 mm by
Sheth and Babu.52 Instead of apparent decomposition rate
expression, the kinetic scheme proposed by Koufopanos
et al.34,35 and validated by many researchers for various
biomasses, is applied. Model simulation results are validated
with the data reported in the literature.45 The proposed
model of the study includes the rate of change of activity
with respect to solid reactant conversion in pyrolysis of
hazelnut-shell biomass. Reaction rate constant is expressed
as a function of extent of reaction, which has replaced the
Arrhenius relation of rate constant with temperature. To
find kinetic parameters of the modified model, an objective
function based on least square error between experimental
data and simulated results has to be minimized. A popula-
tion based search algorithm, differential evolution (DE),
which is simple and robust and has proven successful record,
is employed for optimization in the present case.
Equations in Table 6 show the four different models devel-
oped by Sheth and Babu.52 Model-1 assumes the Arrhenius

Table 6. Mathematical model for kinetic parameter estimation.

Koufopanos et al. (1991) mechanism
Virgin biomass B ( n1 order decay)
Reaction 1 Reaction 2

Reaction 3
( Volatile + Gases)1 + (Char)1 (Volatile + Gases)2 + (Char)2
( n2 order decay) ( n3 order decay)
Residual weight fraction ( W) calculation (n1 = n2 = n3 =1)
W = B + C1 (7)
dB
= − ( k1 + k 2 ) B (8)
dt

dC1
= k1B (9)
dt

dW
= − k1B (10)
dt

T = (HR)t + T0 (11)
Residual weight fraction (W) variation with temperature ( T )
dW 1
= − k1B (12)
dT HR

dB 1
= − ( k1 + k 2 ) B (13)
dT HR

Initial Conditions (at time t=0)

T0 = 325 K; B = 1.0; C1 = 0.0; G1 = 0.0 (14)
Arrhenius relation of kinetic rate constants with temperature ( Model 1)

⎛ −E ⎞ (15)
k1 = A1 exp ⎜ 1 ⎟
⎝ RT ⎠

⎛ −E ⎞
k 2 = A2 exp ⎜ 2 ⎟ (16)
⎝ RT ⎠

Objective function ( Model 1)

( )
n 2
( )
F A1, E1, A2 , E2 = ∑ Wexp, j - Wcal, j (17)
j =1

402 © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
Review: Biomass pyrolysis BV Babu

Table 6. Mathematical model for kinetic parameter estimation. (continued.)

Model 2 ( decrease of frequency factor of pyrolysis rate constants with conversion)

⎛ −E ⎞
( )
k1 = A1 1− z n+1 exp ⎜ 1 ⎟
⎝ RT ⎠
(18)

⎛ −E ⎞
( )
k 2 = A2 1− z n+1 exp ⎜ 2 ⎟
⎝ RT ⎠
(19)

Model 3 ( increase of activation energy of pyrolysis with conversion)

⎡ ⎛ 1+ β ' Tz ⎞ ⎤ (20)
k1 = A1 exp ⎢ − E1 ⎜
⎣ ⎝ RT ⎟⎠ ⎥⎦

⎡ ⎛ 1+ β ' Tz ⎞ ⎤
k 2 = A2 exp ⎢ − E2 ⎜
⎣ ⎝ RT ⎟⎠ ⎥⎦
(21)

where β ' =
βR (22)
E
Model 4 ( increase of activation energy of pyrolysis with conversion)

⎡ ⎛ 1+ β ' Tz n+1 ⎞ ⎤ (23)

k1 = A1 exp ⎢ − E1 ⎜ ⎟⎠ ⎥
⎣ ⎝ RT ⎦

⎡ ⎛ 1+ β ' Tz n+1 ⎞ ⎤
k 2 = A2 exp ⎢ − E2 ⎜ ⎟⎠ ⎥ (24)
⎣ ⎝ RT ⎦

where

⎛ β ⎞R (25)
β' = ⎜
⎝ n + 1⎠⎟ E

Objective function ( Models 2 to 4)

n
(
F ( A1, E1, A2 , E2 , β, n) = ∑ Wexp, j − Wcal, j ) (26)
j =1

relation of kinetic rate constant variation with temperature
(Eqn (7) to Eqn (16)). Equation (16) denotes the objective
function that is the square of error between the experi-
mental data reported by Demirbas 45 and model predicted
values. Models 2 to 4 are based on the fact that the activity
of solid reactant is expected to decrease with the extent of
reaction due to the changes in chemical and pore structure
of solid.
Using DE algorithm, 53,54 the objective function (Eqn (17)
or (26)) is minimized and the global optimum set of kinetic
parameters is found out. To fi nd the theoretical value of
residual weight fraction (W), forward fi nite difference tech-
nique is applied to Eqns (12)–(16) for Model 1. For Model 2,
the theoretical value of residual weight fraction (W) is found
by applying forward finite difference technique to Eqns
(12)–(14) and Eqns (18) and (19). Equations (20) and (21)
are used to fi nd the residual weight fraction of the biomass
for Model 3 along with Eqns (12)–(14). For values of theo-
retical value of W in Model 4, Eqns (23) and (24) are used in
combination with Eqns (12)–(14). Initial conditions used to
solve the above-mentioned fi rst-order differential equations
are given by Eqn (14) in Table 6. Simulations are performed
to fi nd the kinetic parameters of reaction 1 and reaction 2
(A1, E1, A2 , E2 , n, β ) for Model 1 to Model 4 for heating rates
of 10, 25 and 40 K/s for the ground-hazelnut-shell biomass
sample of 0.180 mm size. Figure 2 shows that the Model 3
fits better and gives minimum objective function value for
the heating rate of 40 K/s.

© 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb 403
BV Babu
1.1
1.0
0.9
REsidual Weight Fraction
0.8
0.7
0.6
0.5
0.4
0.3
300 400 500 600
Temperature (K)
Figure 2. Experimental and theoretical residual weight fraction for
various models (heating rate = 40 K/s).
Modeling of biomass pyrolysis
Several researchers have developed the mathematical models
for biomass pyrolysis. Fan et al.55 developed a model for
pyrolysis process, which includes heat and mass transfer
effects in the particle. The reaction, however, is considered
to be first order with respect to the initial particle concen-
tration. The concentration of products cannot be analyzed
from the above model, as the secondary reactions are not
considered. Miyanami et al.56 incorporated the effect of
heat of reaction in the above model. In the Bamford et al.57
model, the equation for heat conduction in a pyrolyzing
solid is combined with that for heat generation, assuming
first order kinetics. However, the effect of density as a func-
tion of time has not been considered in the above model.
This model is modified by Kung58 in order to incorporate the
effects of internal convection and variable transport proper-
ties. However, no specific kinetic mechanism is suggested to
predict the concentration of various components produced
during the pyrolysis process. Kansa et al.59 included the
momentum equation for the motion of pyrolysis gases
within the solid. But, a suitable kinetic mechanism has
not been utilized by them (secondary reactions are not
considered), and the solution to the heat and momentum
balance equation is based on arbitrary boundary condi-
tions. Pyle and Zaror60 used the Bamford et al. 57 model and
404 © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
Review: Biomass pyrolysis
dimensionless groups to define the relative importance of
Expt Data
Model 1 Predicted data the internal and external heat transfer and of the intrinsic
Model 2 Predicted data
Model 3 Predicted data pyrolysis kinetics. They utilized the first order kinetic model
Model 4 Predicted data
based on the density of initial biomass. In the model of
Koufopanos et al.35 the effect of density as a function of time
is not considered while solving the heat transfer equation.
Jalan and Srivastava38 have solved the heat transfer equa-
tion by neglecting the effect of specific heat and thermal
conductivity of char, which are the functions of temperature
as reported by Koufopanos et al.34,35 The convective heat
transfer coefficient is a function of the Reynolds and Prandtl
numbers and is given by h = 0.322 ( k l ) Pr1/3 Re0.5 W/m 2 K,
700 800 900 1000 as reported by Koufopanos et al.35 Jalan and Srivastava, 38
however, have considered that the value of h is constant at
0.322 W/m 2 K, neglecting the effect of other parameters.
Di Blasi25,61,62 pointed out that a detailed transport model
incorporating the kinetics, heat, and mass transfer effects
are necessary to predict the effects of the widely variable
physical properties (density, thermal conductivity, specific
heat capacity) in the pyrolysis of biomass. However, she
used a different kinetic scheme wherein the active cellulose
is considered to be formed as an intermediate product. But
as pointed out by Koufopanos et al.35 it is very difficult to
define physically the components or composition of the
intermediates, and consequently it is not possible to measure
their concentration experimentally in order to test the model
rigorously.
Babu and Chaurasia13 carried out the pyrolysis study on
single solid particle for a wide range of temperature from
303–2700 K and of particle diameter from 0.0005–0.026 m. It
is found that as the particle size increases, the time required
for completion of pyrolysis at a certain pyrolysis temperature
and the effect of secondary reactions increase. It is observed
that, for particle sizes below 1 mm, the process is controlled
by the primary pyrolysis reactions and, possibly, by the
external heat transfer. For particles greater than 1 mm, heat
transfer, primary pyrolysis and secondary pyrolysis control
the pyrolysis process. Babu and Chaurasia13 estimated the
optimum parameters in the pyrolysis of biomass for both
nonisothermal and isothermal conditions. The modeling
equations are solved numerically using the fourth-order
Runge–Kutta method over a wide range of heating rates
(25–360 K/s) and temperatures (773–1773K). The simulated
Review: Biomass pyrolysis
results are compared with those reported in the literature
and found to be in good agreement qualitatively in the range
of operating conditions covered. The final pyrolysis time
first decreases at lower values of net heating rate or tempera-
ture and then increases as net heating rate or temperature
is further increased, providing an optimum value of net
heating rate or temperature at which fi nal pyrolysis time
is minimum.13 The mathematical model to describe the
pyrolysis of a single solid particle of biomass is modified by
incorporating the heat transfer equation with the chemical
kinetics equations in the further study carried out by Babu
and Chaurasia.14 The dependence of convective heat transfer
coefficient on Reynolds number and Prandtl number is
incorporated in the model. A fi nite difference method using
a pure implicit scheme is used for solving the heat transfer
equation and the Runge–Kutta fourth-order method for
the chemical kinetics equations. The model equation is
solved for cylindrical pellets, spheres and slab geometries
of equivalent radius ranging from 0.00025 to 0.013 m and
temperature ranging from 303 to 1000K. The simulated
results obtained using this modified model, are in excellent
agreement with the experimental data, much better than
the agreement with the earlier models reported by Pyle and
Zaror.60 Babu and Chaurasia15 studied the effect of convec-
tive heat transfer and orders of reactions on pyrolysis of
biomass particle using the model developed in their previous
studies.13 The wide ranges of temperature (303–2700 K) and
pellet diameters (0.0005–0.026 m) are considered. It is found
that the pyrolysis is faster for zeroth order as compared
to first order of reaction 1, as the rates are independent of
initial biomass concentration for zeroth order. The effects
of the parameters such as thermal conductivity, reactor
temperature and particle size on product concentrations are
analyzed.48
To describe the chemical process of the pyrolysis
completely, an unsteady state, one-dimensional, variable
property model of transport phenomena, including heat
convection, conduction and radiation, volatiles and gas
transport diff usion and convection and momentum transfer
is required. This generalized reference model is developed
by Babu and Chaurasia16 in their subsequent study of
pyrolysis. A finite difference pure implicit scheme utilizing
a Tri-Diagonal Matrix Algorithm (TDMA) is employed for
© 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
BV Babu
solving the heat transfer and mass transfer model equa-
tions. A Runge–Kutta fourth-order method is used for
the chemical kinetics model equations. Simulations are
performed considering different geometries of equivalent
radius ranging from 0.0001 to 0.017 m and temperatures
ranging from 303 to 2800 K. The results obtained using
these improved models are in excellent agreement with the
experimental data of Pyle and Zaror,60 much better than
the agreement with earlier models reported in the litera-
ture.38,57 The effects of the heat of reaction on the biomass
conversion, concentration, and temperature profi le in the
particle have been analyzed based on the improved model.
The variation in temperature profi le and concentration
profi le for exothermic and endothermic pyrolysis reaction
is explained by using heat of reaction number. Effects of the
most important thermal and thermodynamic properties
(thermal conductivity, heat transfer coefficient, emissivity
and heat of reaction number) of the feedstock on the convec-
tive-radiant pyrolysis of biomass fuels are also carried out
by Babu and Chaurasia.7 Sensitivity analysis is conducted
to find the most dominant properties affecting the pyrolysis
and found that the highest sensitivity is associated with the
emissivity and thermal conductivity of the biomass.7 Simu-
lations are carried out for different geometries considering
the equivalent radius ranging from 0:0000125 m to 0:011 m,
and the temperature ranging from 303 K to 2100 K.15 Effects
of heating conditions, density of biomass, product yields
and conversion on pyrolysis of biomass fuels is studied and
found that the yield of (char)1 increases while the yield of
(volatile and gases)1 decreases as the particle thickness is
increased. There is no effect of density of biomass on both
the primary and secondary reaction products. The conver-
sion time does not depend on the density of biomass and is
nearly constant for complete conversion. Complete conver-
sion of pyrolysis occurs at successively shorter times as the
heating rate is increased. The time required for complete
conversion of pyrolysis is the highest for the slab and lowest
for the sphere.47
The impact of shrinkage on pyrolysis of biomass particles
is studied employing a kinetic model coupled with a heat
transfer model using a practically significant kinetic scheme
consisting of physically measurable parameters.17 The
numerical model is used to examine the impact of shrinkage
405
BV Babu Review: Biomass pyrolysis

on particle size, pyrolysis time, product yields, specific heat (2) Heat transfer occurs by all the three modes (i.e. conduc-
capacity and Biot number considering cylindrical geometry. tion, convection and radiation).
Finite difference pure implicit scheme utilizing TDMA is (3) Gas-phase processes occur under unsteady-state condi-
employed for solving heat transfer model equation. Runge– tions.
Kutta fourth-order method is used for chemical kinetics (4) Transport of mass takes place by convection and diff u-
model equations. Simulations are carried out for radius sion of volatile species.
ranging from 0.0000125 to 0:05 m, temperature ranging (5) Pressure and velocity vary along the porous sample.
from 303 to 900 K and shrinkage factors ranging from 0.0 to (6) Local thermal equilibrium exists between solid matrix
1.0.17 It is found that the temperature profi le of the particle and the flowing gases.
changes due to increased density and decreased distance (7) The system is one-dimensional.
across the pyrolysis region. The magnitude of the tempera- (8) No moisture content and no particle shrinkage.
ture gradient is more for shrinking particles as compared to
Utilizing the kinetic scheme as described by Koufopanos
non-shrinking particles. Shrinkage affects the pyrolysis time
et al.35 and with the assumptions as stated above, the gener-
in thermally thick regime. The pyrolysis conversion process
alized model (Model I) is obtained and reported in Table 7.
is fast for shrinking particles as compared to nonshrinking
The equations shown in Table 7 are written in dimensionless
particles. The modeling and simulation of the above process
forms with the help of dimensionless groups given in Babu
is coupled with the optimization of a nonlinear function
and Chaurasia.17 This generalized model, consisting of Eqns
using DE to find the optimal time of pyrolysis and heating
(38)–(44), which is the most comprehensive one, is named as
rate under the restriction on concentration of biomass. It
Model I (generalized reference model).
serves as the input to the coupled ordinary differential equa-
tions to find the optimum values of volatiles and char using
Simplified models
Runge-Kutta fourth-order method.
These simplified models include additional assumptions
In the present study, therefore, the model developed and
other than those in the generalized reference model
modified by Babu and Chaurasia7,12–17 using physically
(Model I). Many times, in practical situations, the genera-
measurable parameters and a practically explainable kinetic
lized models may not give good predictions. In such cases,
scheme, incorporating the convective and diff usion effects is
there is a need to relax some of the assumptions made in the
presented.
generalized models. Starting from the generalized model,
the following two simplified models are proposed by Babu
Model description of biomass pyrolysis
and Chaurasia17 for specific cases.
Babu and Chaurasia17 proposed three models for the pyrolysis
of biomass under two categories namely, (i) generalized refer-
First simplified model (Model II)
ence model (Model I), and (ii) Simplified models (Model II
The first simplified model (Model II) is proposed by making
and Model III). The three models are presented here briefly
an additional assumption that there is no bulk motion
for clarity and continuity.
contribution (i.e. convective transport is neglected) to the
temperature profile and the product-yield predictions. In this
Generalized reference model (Model I)
treatment, a conservation equation for the mass concentration
The generalized model incorporated all the possible effects
of (gases and volatiles)1 (Eqn (39)) is modified by neglecting
of kinetics, heat transfer, mass transfer, and momentum
the second term on left-hand side. Hence, the first simplified
transfer. The assumptions made in developing this model are
model (Model II) consists of Eqns (38)–(49) and (52).
as follows:

(1) The thermal and transport properties (porosity, thermal Second simplified model (Model III)
conductivity, specific heat, mass diff usivity) vary with The second simplified model (Model III) is proposed on
the conversion level. the following two assumptions concerning the practical

406 © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
Review: Biomass pyrolysis BV Babu

Table 7. Mathematical model.

Koufopanos et al. (1991) mechanism
Virgin biomass B ( n1 order decay)
Reaction 1 Reaction 2

Reaction 3
( Volatile + Gases)1 + (Char)1 (Volatile + Gases)2 + (Char)2
( n2 order decay) ( n3 order decay)
Particle model
Mass conservation for biomass, (gases and volatiles)1 (char)1, (gases and volatiles)2 and (char)2:
∂ CB n n
= − k1CB1 − k 2 CB1 (27)
∂t

∂ (CG1ε ′′ ) ∂ (CG1u ) ⎛ b − 1 ∂ CG1 ∂ 2 CG1 ⎞ n n n

+ = DeG1 ⎜ + + k1CB1 − ε ′′ k 3 CG21CC31 (28)
∂t ∂r ⎝ r ∂r ∂ r 2 ⎠⎟

∂ CC1 n n n
= k 2 CB1 − k 3 CG21CC31 (29)
∂t

∂ CG2 n n
= k 3 CG21CC31 (30)
∂t

∂ CC 2 n n
= k 3 CG21CC31 (31)
∂t

Enthalpy:

∂ ⎛ b − 1 ∂ T ∂ 2T ⎞ ⎛ ∂C ⎞ ∂T ⎛ ∂ρ ⎞
∂t
( )
Cp ρT = k ⎜ +
⎝ r ∂ r ∂ r 2 ⎟⎠ ⎝
− ⎜ DeG1 G1 ⎟ CpG1
∂r ⎠ ∂r
+ ( − ⌬H ) ⎜ − ⎟
⎝ ∂t⎠
(32)

Initial conditions:
t = 0; CB = CB0 , CG1 = CC1 = CG2 = CC 2 = 0, T(r ,0) = T0 (33)

Particle boundary conditions:

∂ CG1 ⎛ ∂T ⎞
t > 0; r = 0, = 0, =0
⎝⎜ ∂ r ⎠⎟ r =0
(34)–(35)
∂r

⎛∂C ⎞
t > 0; r = R, DeG1 ⎜ G1 ⎟ = k mG1 ( CG10 − CG1 ) (36)
⎝ ∂r ⎠

⎛ ∂T ⎞
t > 0; r = R, k⎜
⎝ ∂ r ⎟⎠ r = R
(
= h (Tf − T ) + σε Tf4 − T 4 ) (37)

Dimensionless forms of equations (1)–(11):

∂ CB n n
= − k1C B1 − k 2 C B1 (38)
∂t

n n n
∂ CG1 uR ∂ CG1 DG1 ⎛ b − 1 ∂ CG1 ∂ 2 CG1 ⎞ R 2 k1C B ε ′′R 2 k 3 CG1CC1
1 2 3

ε ′′ + = ⎜ + ⎟ + − (39)
∂τ α ∂x Le ⎝ x ∂ x ∂ x2 ⎠ α α

∂ CC1 n n n
= k 2 C B1 − k 3 CG21CC31 (40)
∂t

∂ CG 2 n n
= k 3 CG21CC31 (41)
∂t

© 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb 407
BV Babu Review: Biomass pyrolysis

Table 7. Mathematical model. (continued.)

∂ CC 2 n n
= k 3 CG21CC31 (42)
∂t

∂θ b − 1 ∂θ ∂ 2θ Q ′′ R 2 k1 1 ⎛ ∂ CG1 ⎞ ∂θ (43)
= + + + DG1 C pG1C B0
∂τ x ∂ x ∂ x2 α Le ⎜⎝ ∂ x ⎟⎠ ∂x

τ = 0; C B = 1, CG1 = CC1 = CG2 = CC 2 = 0, θ (x,0) = 1 (44)

∂ CG1 ∂θ
τ > 0; x = 0, = 0, =0 (45)–(46)
∂x ∂x

⎛ ∂ CG1 ⎞
τ > 0; x = 1, DG1 ⎜ = Sh( CG10 − CG1 ) (47)
⎝ ∂ x ⎟⎠

∂θ (48)
τ > 0; x = 1, = −θ BiM
∂x

Koufopanos et al. (1991) correlation:

h = 0.322 ( k l ) Pr 1/ 3 Re0.5 (49)

Darcy law and state equation:

φ ∂p (50)
u=−
µ ∂x

p = CG1Rc T Wm (51)

Other relations:

ε ′′ = ε 0 ′′ + γ (1− C B ), φ = ηφB + (1− η )φC1, η = CB CB0 (52)–(54)

Conversion of biomass:

C B0 − ⎡⎢⎛⎜ ∑ CB ⎞⎟ ⎤
M
( M +1) ⎥
⎣⎝ i = 1 ⎠ ⎦ (55)
X=
C B0

applications: (i) The basic mode of transfer inside the solid Interestingly, this is similar to the model proposed by the
particle in the process of pyrolysis is by conduction heat Babu and Chaurasia in their earlier study,13 which means
transfer only; and (ii) the effect of porosity of the solid that the generalized reference model reduced to the model
particle is negligible. Based on these assumptions, the proposed by Babu and Chaurasia13 under specific conditions.
conservation equation for the mass concentration of (gases
and volatiles)1 (Eqn (39)) and heat transfer model (Eqn (43)) Numerical solution and simulation
become: Equations (39) and (43) along with the initial and boundary
conditions given by Eqns (44)–(50) were solved numerically
∂ C G1 n n n by finite difference method using pure implicit scheme.17 The
= k1 C B1 − k3 C G21 C C31 (56)
∂t pure implicit scheme is an unconditionally stable scheme,
i.e. there is no restriction on the time-step in sharp contrast
∂θ b − 1 ∂θ ∂ 2θ Q n R 2 k1 (57)
= + + with the Euler and Crank-Nicholson method as discussed by
∂τ x ∂x ∂x2 α
Ghoshdastidar.63 The Eqns (38)–(43) are solved simultane-
Thus, the second simplified model (Model III) consists ously. Equations (38), (40), (41), and (42) are solved by the
of Eqns (38), (56), (40)–(42), (57), (44), (46), (48), and (49). Runge-Kutta fourth-order method with both the fi xed-step

408 © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
Review: Biomass pyrolysis
size and the variable-step size. It is found that the Runge-
Kutta fourth-order variable-step-size method (RKVS) is
faster than the Runge-Kutta fourth-order method with
fi xed-step size (RKFS), as discussed by Babu and Angira.64
The RKVS method, however, does not give the solution for a
particular and fi xed interval of time. The discretized form of
Eqns (39) and (43) were solved by TDMA, also known as the
Thomas Algorithm.
Figure 3 shows the conversion profi le as a function of time
with the cylindrical pellet of radius 0.00915 m and fi nal
temperature of 679 K. The model developed is in better
agreement for experimental data of Alves and Figueiredo65
also when compared with the model of Liliedahl and
Sjöström.66 It overpredicts the conversion at higher values
of the pyrolysis time. This may be due to the fact that
while developing the model, Liliedahl and Sjöström66 did
not consider the variation of thermal conductivity and the
specific heat capacity of biomass with temperature.
Measurements of product distribution for different sized,
single, cellulose particles are not available to make quanti-
tative comparisons with the model predictions. However,
cellulose pyrolysis in the fluid-bed and entrained-flow reac-
tors67 and in low-temperature vacuum-tube furnace 68 is
considered for comparison and some conclusions are drawn.
To this end, the experimental data have been replotted
together with the simulation results, obtained for a particle
half-thickness of 0.0000125 m (thermally thin regime) as
100 LEGEND
Alves & Figueiredo (1989) (Experimental)
90 Babu & Chaurasia (2003a)
80 Liliedahl & Sjostrom (1998)
70
Conversion (%)
60
50
40
30
20
10
0 0
0 100 200 300 400 500 600
Time (s)
Figure 3. Conversion profile as a function of time with cylindrical
pellet (R = 0.00915 m, T0 = 303 K, Tf = 679 K).
© 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
BV Babu
shown in Fig. 4. Since in both the experiments, very thin
particles (powder) by Shafi zadeh et al.68 and the particle
sizes of about 100 μm by Scott et al.66 are used, it can be said
that the intraparticle resistance to heat transfer is negligible.
As shown, the match between the model and the experi-
mental data is very good.
Babu and Chaurasia17 carried out simulations for the
temperature ranging between 303 K and 2100 K and the
equivalent particle radius ranging between 0.0000125 m
and 0.011 m. The pyrolysis rate was obtained by considering
two parallel primary reactions and a third, secondary reac-
tion between the volatile and gaseous products and char.
It is found that the secondary reactions are responsible
for carbon enrichment of the fi nal residual. The effects of
the parameters, such as heat of reaction number, thermal
conductivity, heat transfer coefficient, emissivity, and reactor
temperature, were analyzed. The results obtained from the
model13 were in good agreement with many experimental
results60,65,67,68 as compared to the model developed by
the earlier researchers.38,59 It is found that the production
of (char)1 is favoured by the endothermic reactions while
the production of (volatile and gases)1 is favoured by the
exothermic reactions. It is also found that the conversion
time becomes successively longer as the thermal conduc-
tivity of biomass increases and/or emissivity decreases, thus
affecting the reactor throughput. It is observed that the
feedstocks with lower thermal conductivity produce a gas of
100
90
80
70 Babu & Chaurasia (2003a)
Shafizadeh et al. (1979a) (Experimental)
60
Yield (%)
Scott et al. (1988) (Experimental)
50
40
30
20
CHAR
10
600 650 700 750 800 850 900
Temperature (K)
Figure 4. Average char yield as a function of temperature for particle
half-thickness of 0.0000125 m.
409
BV Babu
better quality for a fi xed particle size. Babu and Chaurasia17
also performed sensitivity analysis for most of the variables
and it is found that convective heat transfer coefficient
is the least sensitive parameter and sensitivity for all the
parameters is highest for the slab geometry and is lowest for
the spherical geometry. The results obtained by Babu and
Chaurasia17 have a lot of practical importance and physical
significance in industrial pyrolysis applications. The results
are also important and useful for design of biomass gasifiers,
reactors, etc.
Thermal plasma pyrolysis
Thermal plasma pyrolysis can be described as the process
of reacting a carbonaceous solid with limited amounts of
oxygen at very high temperature to produce gas and solid
products. In the highly reactive plasma zone, there is a large
fraction of electrons, ions and excited molecules together
with the high-energy radiation. When carbonaceous parti-
cles are injected into plasma, they are heated very rapidly by
the plasma; and the volatile matter is released and cracked
giving rise to hydrogen and light hydrocarbons such as
methane and acetylene.69 There are four stages that can be
distinguished in the thermal plasma pyrolysis process:
Stage 1: A very fast heating of the particles as a result of
their heat exchange with the plasma jet.
Stage 2: An explosive liberation of volatile matter from the
particles.
Stage 3: A very quick gasification of the homogeneous phase
and rapid heat and mass exchange.
Stage 4: Further gasification of char particles with various
gaseous components.
A reaction scheme proposed by Huang et al.70 for rubber
pyrolysis in a dc arc plasma can be divided in four stages as
described below:
In Stage 1, primary pyrolysis reactions take place and the
volatile matter is released including heavy hydrocarbons
(tar), light hydrocarbons, and other gaseous components,
leaving behind solid char.
Rubber → char + heavy hydrocarbons + light hydrocarbons
+ gas (H2 ,CO,CH4 ,C 2H2 ,C 2H4 , etc.)
(58)
410 © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb
Review: Biomass pyrolysis
In Stage 2, tar gets cracked and light hydrocarbon may also
decompose.
heavy hydrocarbons → light hydrocarbons +
gas (H2 ,CO,CH4 ,C 2H2 ,C 2H4 , etc.)
(59)
light hydrocarbons → H2 +CH4 +C 2 H2 +C 2 H4 +C n Hm
(60)
In Stage 3, light hydrocarbons may further decompose.
This stage could be replaced by quench technology in order
to achieve certain technical purposes such as monomer
recovery.
In Stage 4, addition of water/steam could be effectively
used to promote syngas (H2 and CO) production.
char + H2O → CO + H2 + solid residue (61)
This could be one of the reasons for the observation that
H2 and CO concentrations were increased, and solid yield
decreased with steam injection. The solid residue includes
the inorganic tire component, carbon black fi ller, and
carbonaceous deposit.70
Nema and Ganesh Prasad71 proposed following reac-
tions for the plasma pyrolysis of simulated medical waste
(containing cellulose and polyethylene).
C6H10O5 + heat → CH4 + 2CO + 3H2O + 3C (62)
[–CH2 – CH2 –]n + H2O + heat → xCH4 + yH2 + zCO (63)
High temperature combined with the high heating rate
of the plasma results in the destruction of organic waste,
giving rise to a gas and a solid residue with varied proper-
ties depending on the feed characteristics and operating
conditions.72
Reaction mechanisms of plasma-assisted
pyrolysis
The pyrolysis mechanisms of polymer molecules, which
may comprise tens of thousands of atoms, are very complex.
Pyroly tic reactions have been broadly classified into four
groups: random main-chain scission, depolymeriza-
tion, carbonization, and side-group reactions. Random
main-chain scission is defined as the breaking of the
Review: Biomass pyrolysis BV Babu

main chain to produce smaller molecules of random sizes. Kinetic modeling of plasma pyrolysis
Depolymerization is defi ned as the successive removal of
Experimental studies on plasma pyrolysis have been
monomer units from the chain and leads to the formation of
conducted by many researchers using a variety of raw mate-
free radicals and chain reactions. Carbonization and side-
rials, such as agricultural residue, waste tyre, municipal
group reactions include those reactions which lead to cross-
solid waste etc. 69–74 Understanding the physical phenomena
linking, straight-chain-polymer formation by elimination of
of plasma-assisted pyrolysis and representing them with an
side chains, cyclization, and aromatization by dehydrogena-
appropriate mathematical model is essential in the design of
tion. According to free-radical chain-reaction theory, both
reactors.
chain scission and depolymerization mechanisms involve
Shuangning et al.75 developed a plasma heated laminar
initiation, propagation, chain transfer, and termination
entrained flow reactor (PHLEFR) in order to study the vola-
reactions.
tilization characteristics of biomass particles at flash heating
Based on the standard Gibbs free-energy changes for the
rates. A simple kinetic model is proposed in order to predict
reactions, it is found that energy requirement for carbon–
the reaction rate for a wide range of operating conditions
carbon bond cleavage is less than that for dehydrogenation.
and various biomasses. The conversion process is mathemati-
At a given temperature, chain scission of C–C bonds at the
cally expressed by a following equation.
ends of molecules is more probable than at the center of
the molecule. Removal of hydrogen by breaking C-H bond E
dα −
= Ae RT (1 − α ) (64)
from CH3, C2H5, n-C3H7 requires 435.2 kJ/mol, 410 kJ/mol dt
and 408.4 kJ/mol of energy respectively, whereas to remove
where α is the fraction of reactant decomposed at resi-
hydrogen from CH2=CHCH2 requires only 363.2 kJ/mol of
dence time t. A and E are the apparent frequency factor (s–1)
energy. Removal of CH3 by breaking C-C bond from CH3,
and apparent activation energy (kJ/mol), respectively; R is
C2H5, n-C3H7 requires 369.9 kJ/mol, 353.6 kJ/mol and 355.2
the universal gas constant, 8.3145 (J/mol); T is the absolute
kJ/mol of energy respectively, whereas to remove CH3 from
temperature (K) of the pyrolytic process. The fractional
CH2=CHCH2 requires only 307.9 kJ/mol of energy.73 Based
reactant α is defined as the ratio of W to W ∞, where W is the
on the bond dissociation energies of C–C and C–H bonds, it
volatile mass fraction at time t; W ∞ is the maximum volatile
is found that the C–C and C–H bonds to the allylic carbon
mass fraction (in wt%). The kinetic model presented here was
are weaker than the corresponding bonds in a pure saturated
fitted to the experimental data and kinetic parameters are
chain. These bonds are β-bonds with respect to the double
found (Table 8). Shuangning et al.75 studied the volatiliza-
bond and their scission is known as β-scission. All chain
tion characteristics of biomass particles at flash heating rates
ends of heavy molecular weight polyethylene have β-bond.
and developed and validated the kinetic model and found
Collisions between the polymer molecules and electrons
the kinetic parameters for the various agricultural residues.
and ions from the plasma initiate the β-scission process
However this analysis is not reported in the literature for
in plasma reactor. Propagation occurs through a series of
other carbonaceous wastes and also the model developed by
reactions which convert the polymer fragments into reac-
Shuangning et al.75 is not improved to incorporate the effects
tants and, subsequently, to final products through radical
decomposition, radical isomerization, hydrogen transfer,
and/or radical addition. Termination reactions occur when Table 8. Kinetic parameters of biomass pyrolysis
reaction determined with PHLEFR.
two radicals combine or are disproportionate to form stable
products.73 The range of product compositions obtained Raw materials A (s−1) (103) E (kJ/mol)
will depend on both the relative sensitivity of secondary Wheat straw 1.05 31.63

versus primary reactions to changes in temperature and the Coconut shell 6.84 48.73

residence time of the material within the high-temperature Rice husk 1.19 39.30

plasma region. Cotton stalk 2.44 40.84

© 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb 411
BV Babu
of various parameters, such as feed rate, size of the parti-
cles, heating rate, thermal and thermodynamic properties
(thermal conductivity, heat transfer coefficient, emissivity
and heat of reaction number) of the feedstock on the convec-
tive-radiant pyrolysis of biomass fuels.
There is a lot of scope for improving the existing models
on plasma pyrolysis by incorporating simultaneous effects
of heat, mass and momentum in combination with reaction
kinetics. There is also a need to make use of CFD (compu-
tational fluid dynamics) simulations to have a better under-
standing of the physical phenomena occurring in plasma
pyrolysis at microlevel.
Conclusions
• The pyrolysis of biomass is a promising route for the
production of solid (charcoal), liquid (tar and other
organics) and gaseous products (H2 , CO2 , CO).
• Modeling and simulations are required to describe the
pyrolysis mathematically. It would be useful to predict
the product-gas concentration for various operating
conditions and for a variety of feed mixtures. To design
a suitable pyrolysis reactor, modeling and simulation of
pyrolysis are very important.
• There is a tremendous scope for applying plasma-assisted
pyrolysis of assorted non-nuclear waste, such as biomass,
printed circuit boards, organic waste, medical waste etc.,
for obtaining useful energy.
• There is a need to improve upon the existing simple
models on plasma pyrolysis by incorporating simulta-
neous effects of heat, mass and momentum in combina-
tion with reaction kinetics. CFD simulations would
enhance the understanding of physical phenomena
occurring in plasma pyrolysis.
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Technology Division, Bhabha Atomic Research Centre (BARC), Mumbai, 75. Shuangning X, Weiming Y and Baoming L, Flash pyrolysis of agricultural
September 18 (2007). residues using a plasma heated laminar entrained flow reactor. Biomass
70. Huang H, Tang L and Wu CZ, Characterization of gaseous and solid Bioenerg 29:135–141 (2005).
product from thermal plasma pyrolysis of waste Rubber. Environ Sci
Technol 37:4463–4467 (2003).
71. Nema S and Ganesh Prasad KS, Plasma pyrolysis of medical waste. Curr B. V. Babu
Sci India 83:271–278 (2002).
Dr B. V. Babu is Professor of Chemical Engineering
72. Huang H and Tang L, Treatment of organic waste using thermal plasma
and Dean of Educational Hardware Division at BITS-
pyrolysis technology. Energ Convers Manage 48:1331–1337 (2007).
Pilani, India. He has 23 years of teaching, research,
73. Guddeti RR, Knight R and Grossmann ED, Depolymerization of
consultancy, and administrative experience. He
Polyethylene Using Induction-Coupled Plasma Technology. Plasma
has around 150 research publications to his credit in the areas of
Chem Plasma P 20:37–64 (2000).
energy and environmental engineering, evolutionary computation,
74. Hung-Lung C, Kuo-Hsiung L, Mei-Hsiu L, Ting-Chien C and Sen-Yi M,
and modeling and simulation. He has published five books, and
Pyrolysis characteristics of integrated circuit boards at various particle
has written several chapters.
sizes and temperatures, J Haz Mat (In press 2007).

414 © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:393–414 (2008); DOI: 10.1002/bbb