BY

C.VIJAY
2014017025
 Pyrolysis is essentially the thermal
decomposition of organic matter under inert
atmospheric conditions or in a limited supply
of air, leading to the release of volatiles and
formation of char. Pyrolysis in wood is
typically initiated at 200oC and lasts till 450-
500oC, depending on the species of wood
 Pyrolysis has an important role in the
combustion of wood and sawdust since the
products of this stage, namely, volatiles and
char, subsequently undergo flaming and
glowing combustion respectively to release
thermal energy.
 The physical process
 The basic phenomena that take place during
pyrolysis are: heat transfer from a heat
source leading to an increase in temperature
inside the fuel; initiation of pyrolysis
reactions due to this increased temperature
leading to the release of volatiles and the
formation of char; flow of volatiles towards
the ambient resulting in heat transfer
between hot volatiles and cooler unpyrolysed
fuel
 The chemistry of pyrolysis is strongly
influenced by the chemical composition of
the fuel. The elemental composition of the
fuel may be obtained from ultimate analysis.
A fair idea of the percentage of the major
products of pyrolysis weight. It is to be noted
that volatiles are almost 77% by weight of dry
wood.
The major constituents of biomass are
 cellulose (a polymer glucosan),
 Hemicellulose(a polysaccharide producing

wood sugars),
 lignin (a multi-ring organic compound).
 Cellulose is a glucon polymer consisting of
linear chains of B(1,4) d-glucopyranose units.
Its average molecular weight is 100,000.
Aggregation of these linear chains within the
microfibrils provides a crystalline structure
that is highly inert and inaccessible to
chemical reagents. Cellulose component
normally constitutes 45-50% of the dry wood.
Shafizadeh has studied the pyrolysis of
cellulose as the temperature is increased
 Hemicellulose is a mixture of polysaccharides
mainly composed of glucose, mannose,
galactose, xylose, arabinose, 4-0
methylglucuronic acid and galacturonic acid
residues. Generally, it is of much lower molecular
weight than cellulose and is amorphous in
structure unlike cellulose. Its content varies from
20 to 40%. According to Soltes and Elder ,
hemicellulose is thermally most sensitive and
decomposes in the temperature range 200oC to
260oC.
 This decomposition may occur in two steps;
decomposition of the polymer into soluble
fragments and/or conversion into monomer
units that further decompose into volatile
products. As compared to cellulose,
hemicellulose gives rise to more volatiles,
less tar and char. The components of tar are
organic acids such as acetic acid, formic acid
and a few furfural derivatives
o Lignin is amorphous in nature and a random
polymer of substituted phenyl propane units
280oC and 500oC. Char is the more abundant
constituent in the products of lignin pyrolysis
with a yield of 55%. A liquid product known
as pyroligneous acid consists of 20% aqueous
components and 15% tar residue on dry lignin
basis. The aqueous portion is composed of
methanol, acetic acid, acetone and water.
 The overall process of pyrolysis of wood is
believed to proceed as follows. At around
160oC the removal of all moisture
(dehydration) is complete. Over the
temperature range 200oC to 280oC, all the
hemicellulose decomposes, yielding
predominantly volatile products such as
carbon dioxide, carbon monoxide and
condensable vapours. From 280oC to 500oC
the decomposition of cellulose picks up and
reaches a peak around 320oC.
 Most Biomass has a cellular structure with
extensive voids, such that while the density
of the lignocellulosic cell wall material
typically is between 1.5-2 g/cm3, the density
of wood ranges between 0.2-1.3g/cm3. As a
result, the heat transfer characteristics are
very poor characterised by the biot number.
Gas – non-condensable gases like carbon
dioxide, carbon monoxide, hydrogen
 Solid – mixture of inorganic compounds (ash)

and carbonaceous materials (charcoal)

 Liquid – mixture of water and organic

compounds known as bio-oil recovered from

pyrolysis vapors and aerosols (smoke)
 SLOW PYROLYSIS
 FAST PYROLYSIS
 The slow heating in the absence of oxygen to
temperatures in excess of 400°C induces the thermal
decomposition of lignocellulosic biomass producing
approximately equal masses of syngas, bio-oil, and
biochar.
 In traditional, charcoal kilns the syngas and the
pyrolysis vapors (a multi-phase liquid formed by a
decanted oil and pyrolygneous water when
condensed) are vented to the atmosphere often
creating serious air pollution hazards.
 Biochar produced in traditional kilns is commonly
commercialized as a fuel for domestic cooking and
heating or used in the metallurgical industry.
 The world production of biochar in 2005 was more
than 44 million tons
 During fast pyrolysis, biomass is rapidly (<1 s)
heated to 400-700°C in the absence of oxygen.
 To achieve such rapid heating rates the particle
size of the feedstock must generally be reduced
to < 2 mm, which requires significant amounts of
energy.
 The primary energy product, bio-oil, is a dark
brown liquid obtained by condensation of the
pyrolysis vapor.
 Fast Pyrolysis yields 60-70 mass percent of the
original biomass as bio-oil and 15-25 mass
percent as biochar. The overall energy recovery
of fast pyrolysis depends critically on the
moisture content of the biomass feedstock.
 Type A: No solid movement through the reactor
during pyrolysis (batch reactors)
 Type B: Moving bed (shaft furnaces)
 Type C: Movement caused by mechanical forces
(e.g., rotary kiln, rotating screw etc.)
 Type D: Movement caused by fluid flow (e.g.,
fluidized bed, spouted bed, entrained bed etc.)
 Charcoal making today is mostly based on Type
A and Type B reactors, Type A reactors are more
common in developing countries.
 It is the simplest type of reactor. The
immobilized enzyme is placed in a container
with the reactants, and the reaction is allowed
to proceed until the desired level of
conversion is reached.
 Some stirring or agitation of reaction mixture

is also required. Many modifications of these

reactors have been designed to simplify
recovery and reuse of the enzyme composite.
 These types of reactors employ a stirred tank,
to which reactants are continuously added
and products continuously withdrawn.
 In these reactors, enzyme system is fluidized
by the upward flowing of substrate solution.
This helps in eliminating any plugging of
enzyme system, although small duration of
contact may be insufficient for the desired
conversion.
 These are most widely used for large scale
commercial operations. These reactors will
keep on dominating the large scale
commercial application due to their high
efficiency and ease and simplicity of
operation.
 Bubbling fluidized bed
 Circulating fluidized beds/transport reactor
 Rotating cone pyrolyzer
 Ablative pyrolyzer
 Vacuum pyrolysis
 Auger reactor
 Heat supplied externally to bed
 Good mass & heat transfer
 Gas residence times shorter than char residence
times
 Small particle sizes of less than 2-3 mm are
needed
 Shallow beds and/or a high gas flow rates are
needed to achieve short volatiles residence times
 The high gas-to-biomass fed ratio results in a
lowering of the thermal efficiency (which is
typically 60-70%)
 Sand and biomass brought into contact within
rotating cone
 Compact design and does not need carrier

gas
 Requires very small biomass particles and is

hard to scale-up
High pressure of particle on hot reactor wall
achieved by centrifugal or mechanical motion
 Can use large particles and does not require

carrier gas
 Complex and does not scale well
Biomass moved by gravity and rotating
scrappers through multiple hearth pyrolyzer
with temperature increasing from 200 C to
400 C
 Can use larger particles and employs little

carrier gas
 Expensive vacuum pump and difficult to

scale-up
Hot sand and biomass mixed by auger
 Suitable for small scale
 Requires hot sand heating and circulation

system
 No heat carrier
 Little to no carrier gas
 Simple design –no moving parts
 Requires small biomass particles
 May be suitable for distributed pyrolysis

operations and small scale

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