Biomass Pyrolysis

D.Nagaraju
Assistant Professor
Mechanical Engineering Department
 CONTENT
▪ Introduction
▪ Types of Pyrolytic Reactors
▪ Parameters Influencing Pyrolysis Process
▪ Mechanism and Products of Biomass
Pyrolysis
▪ The Charcoal Making Process
▪ Factors Influencing The Charcoal Yield
▪ Different Types Of Charcoal Kiln

3
 INTRODUCTION
• Overview
– Pyrolysis is defined as irreversible chemical change
brought about by heat in the absence of oxygen.
– During pyrolysis biomass undergoes a sequence of
changes and normally yields a mixture of gases,
liquids and solid.
– The solid is called charcoal while the condensable
liquid is variously referred to as pyroligneous liquid,
pyroligneous liquor, pyroligneous acid or pyrolysis
oil. The gas is called producer gas or wood gas.
– Generally low temperatures and show heating rates
results in high yield of charcoal. This type of
pyrolysis is called carbonization
 INTRODUCTION
• Overview
– In a now obsolete process for production of
methanol, acetic acid and acetone, wood is heated in
a retort in absence of air and the liquid vapours are
condensed.
✓ This type of pyrolysis is generally called destructive
distillation.
– In a relatively recent development it is found that
yields of volatiles (gas and liquid) increase with the
rate of heating. At sufficiently high heating rates all
biomass can be nearly converted to volatiles.
✓ This is known as fast pyrolysis.
– Although pyrolysis (as a process for charcoal
making) has been known to man since time
immemorial, the complex pattern of series and
parallel reactions involved in the process is not yet
fully understood.
 INTRODUCTION
• Pyrolysis Technology Variant
– Pyrolysis processes classified based on heating
rates and residence time
Process Residence Heating Temp Products
Time Rate (C)
Carbonization Days Very low 400 Charcoal
Conventional 5 – 30 min Low 600 Oil, Gas, Char
Fast 0.5 – 5 sec Very high 650 Bio-oil
Flash-liquid < 1 sec High <650 Bio-oil
Flash-gas < 1 sec High <650 Chemicals, Gas
Ultra < 0.5 sec Very high 1000 Chemicals, Gas
Vacuum 2- 30 sec Medium 400 Bio-oil
Hydro-pyrolysis < 10 sec High <500 Bio-oil
Methano- < 10 sec High >700 Chemicals
pyrolysis
TYPES OF PYROLYTIC REACTORS
• System Configuration
– A pyrolysis system unit typically consists of the
equipment for biomass pre-processing, the pyrolysis
reactor, and equipment for downstream processing.
– Can be classified as units that produce heat and
biochar (using slow pyrolysis) or units that produce
biochar and bio-oils (using fast pyrolysis),
Gas
Heat
Condensers

Air
Biomas
Pyrolysis Combustion Combustion
vapors Biomas
s Chamber Gases
s
Pyrolysis
vapors
PYROLYSIS PYROLYSIS
REACTORS Bio-oil
REACTORS
Char Char

(a) Biochar and bio-oil production (b) Biochar and heat production
TYPES OF PYROLYTIC REACTORS
• Classification based on solid movement
– Reactors used for biomass pyrolysis is most
commonly classified depending on the way the solids
move through the reactor during pyrolysis.
✓ 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.)
TYPES OF PYROLYTIC REACTORS
• Classification based on method of heat
supplied
– Pyrolytic reactor can also be classified depending the
way heat is supplied to biomass:
✓ Type 1:
Part of the material burnt inside the reactor to provide the heat
to carbonize the remainder
✓ Type 2:
Direct heat transfer from hot gases produced by combustion
of the pyrolysis products or any other fuel outside the reactor.
✓ Type 3:
Direct heat transfer from inert hot material (hot gases or sand
introduced into the reactor).
✓ Type 4:
Indirect heat transfer through the reactor walls (i.e. external
heat source due to combustion of one or more pyrolysis
products or any other fuel).
TYPES OF PYROLYTIC REACTORS
• Variations in the Process and Reactors
– Many different combinations of modes of solid
movement and modes of heat transfer are possible in
practice.
– Accordingly, the type of a pyrolytic reactor can
probably be best specified by denoting it as type XI
where X stands for type of solid movement and I
indicates the type of heat transfer.
– Different names are often used to describe specific
type of pyrolytic reactors.
✓ The term “kiln” is used for devices producing only charcoal.
✓ The terms “retort” and “converter” are used for equipment's
capable of recovering by-products.
✓ The term “converter” normally refers to devices used for
pyrolyzing biomass of small particle size and the term “retort”
refers to equipment for pyrolysing log reduced in size to about
30 cm length and 18 cm diameter.
TYPES OF PYROLYTIC REACTORS
• Types of Pyrolysis Reactor Designs
– A number of different pyrolysis reactor designs are
available.
– These include Fluidized bed, Re-circulating fluidized
bed, Ablative, Rotating cone, Auger (or screw),
Vacuum, Transported bed, and Entrained flow.

Fluidized bed

Rotating cone
TYPES OF PYROLYTIC REACTORS
• Types of Pyrolysis Reactor Designs

Re-circulating
fluidized bed

Vacuum
TYPES OF PYROLYTIC REACTORS
• Types of Pyrolysis Reactor Designs
– As pyrolysis is a precursor to gasification and
combustion, the same reactors used for gasification
can be used for pyrolysis.
– Bubbling fluidized bed reactors are simpler to design
and construct than other reactor designs, and have
good gas to solids contact, good heat transfer, good
temperature control, and a large heat storage
capacity.
– Circulating fluidized bed pyrolysis reactors are
similar to bubbling fluidized bed reactors but have
shorter residence times for chars and vapors which
results in higher gas velocities, faster vapor and char
escape, and higher char content in the bio-oil.
– They have higher processing capacity, better gas-
solid contact, and improved ability to handle solids
that are difficult to fluidize.
TYPES OF PYROLYTIC REACTORS
• Heat Transfer Modes and features of
various reactors:
Reactor Mode of heat Typical features
type transfer
Fluidized 90% conduction; High heat transfer rates; Heat supply to fluidizing gas or to bed
bed 9% convection; directly; Limited char abrasion; Very good solids mixing;
1% radiation Particle size limit < 2 mm in smallest dimension; Simple reactor
configuration
Circulating 80% conduction; High heat transfer rates; High char abrasion from biomass and
fluidized 19% convection; char erosion; Leading to high char in product; Char/solid heat
bed 1% radiation carrier separation required; Solids recycle required; Increased
complexity of system; Maximum particle sizes up to 6 mm;
Possible liquids cracking by hot solids; Possible catalytic
activity from hot char; Greater reactor wear possible
Entrained 4% conduction; Low heat transfer rates; Particle size limit < 2 mm; Limited
flow 95% convection; gas/solid mixing
1% radiation
Ablative 95% conduction; Accepts large size feedstocks; Very high mechanical char
4% convection; abrasion from biomass; Compact design; Heat supply
1% radiation problematical; Heat transfer gas not required; Particulate
transport gas not always required
 PARAMETERS INFLUENCING
PYROLYSIS PROCESS
• The basic phenomena that take place
during pyrolysis:
– 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;
– Outflow of volatiles, resulting in heat transfer
between the hot volatiles and cooler unpyrolysed
fuel;
– Condensation of some of the volatiles in the cooler
parts of the fuel to produce tar; and
– Autocatalytic secondary pyrolysis reactions due to
these interactions.
 PARAMETERS INFLUENCING
PYROLYSIS PROCESS
• Pyrolysis process control parameters:
– Important pyrolysis process control parameters
include:
✓ Heat rate (length of heating and intensity),
✓ Prevailing temperature and pressure
✓ The presence of ambient atmosphere
✓ The chemical composition of the fuel (e.g., the biomass
resource),
✓ Physical properties of the fuel (e.g. particle size, density),
✓ Residence time and the existence of catalysts.
– These parameters can be regulated by selection
among different reactor types and heat transfer
modes, such as gas–solid convective heat transfer
and solid–solid conductive heat transfer.
THE CHARCOAL MAKING PROCESS
• Basics
– Charcoal is made in many different ways depending on the type
of reactor employed.
– However, the basic steps by which wood is transformed to
charcoal are the same.
– Three distinct phases can be distinguished: drying, pyrolysis,
and cooling.
– In practice, and particularly when the charcoal is made in large
kilns, there is often a considerable overlap between these.
– Thus, pyrolysis may be well advanced in one area of the kiln
before drying is complete in another.
THE CHARCOAL MAKING PROCESS
• The Drying Phase
– Before wood can be carbonized, the water it contains
must be driven off. This happens in two distinct
stages:
✓ The first is when the water in the pores of the wood,
sometimes called the free water, is expelled. While this is
happening, the temperature of the charge of wood remains at
about 110C. The wetter the wood, the longer this process
takes and the greater is the amount of energy consumed
during it.
✓ When all the water in the pores has been driven off, the
temperature rises. When it reaches about 150C, water which
is more tightly bound or absorbed into the cellular structure of
the wood (bond water) begins to be released. This continues
as the temperature rises to around 200C.
✓ When the charcoal is made in a kiln, the water is released to
the air in the form of water vapour. This is the principal
constituent of the white smoke characteristic of the early
stages of carbonization.
THE CHARCOAL MAKING PROCESS
• The Pyrolysis Phase
– With the continued application of heat, the
temperature of the wood rises further.
– Around 280C, the pyrolysis reaction begins to occur.
The breakdown of biomass results in the evolution of
a complex series of chemical substances referred to
as the pyrolysis products.
– Because most of these are driven off in the form of
gas or vapour, they are often described as the
volatiles.
– The presence of the volatiles causes the colour of the
smoke coming from a charcoal kiln to darken thus
indicating that pyrolysis is under way.
– It also gives rise to the characteristic heavy smell of
wood-tar normally associated with charcoal making.
THE CHARCOAL MAKING PROCESS
• The Pyrolysis Phase
– Once the pyrolysis is under way, the need for a heat
supply to maintain the reaction is very much less
than that needed to drive off the water during the
drying phase.
– When using a kiln, the need to continue burning part
of the charge is reduced and the air supply is usually
restricted at this stage.
– The temperature reached during pyrolysis depends
on the size of the charge of wood being carbonized,
the geometry of the kiln, the degree to which the
manufacturing process is insulated against heat loss,
the ambient temperature, the original moisture
content of the wood, and a variety of other factors.
THE CHARCOAL MAKING PROCESS
• The Pyrolysis Phase
– In most small-scale traditional methods of
manufacture, the maximum temperature reached
tends to be about 400-500C. But in some types of
kilns, temperatures of up to 600-700C are attained.
Higher temperatures normally require the use of
retorts.
– During pyrolysis, there is a considerable loss of
volume in the wood. Across the grain this can be as
much as 30-40%, though it is much less along the
grain.
– A kiln in which the wood has been laid horizontally
thus tends to collapse down wards during charcoal
making, whereas on in which the wood has been
stacked vertically has a much smaller change in
volume.
THE CHARCOAL MAKING PROCESS
• The Cooling Phase
– As the pyrolysis reaction draws to its completion, the
temperature in the charge of wood begins to fall.
– The amount of smoke given off from a charcoal kiln
drops substantially and its colour changes to a pale
blue and in some cases the smoke emission stops
completely.
– The kiln or retort must be kept tightly sealed at this
stage. If air is admitted before the charcoal has fallen
below its ignition temperature, there is a danger of
the whole load bursting into flame.
– Even when it has been allowed to cool thoroughly,
care must always be taken as the charcoal is being
unloaded from the kiln. High temperature pockets
often remain and these can ignite spontaneously as
they come into contact with air.
THE CHARCOAL MAKING PROCESS
• The Cooling Phase
– Once it has been released to the open air, charcoal is
usually left for a period of about 24 hours for
‘seasoning’ to occur.
– During this time, the charcoal cools to air
temperature and some of the remaining volatiles
escape. Some moisture and a small amount of
oxygen are also absorbed.
– Once the danger of spontaneous combustion
disappears and the charcoal is ready for packing and
transport.
 FACTORS INFLUENCING THE
CHARCOAL YIELD
• Factors
– A number of factors affect the yield of charcoal
obtained from a particular manufacturing method.
– Two of the most important of these are the maximum
temperature reached during carbonization and the
moisture content of the wood
• Carbonization Temperature
– The carbonization temperature affects the yield as
well as the fixed carbon content.
– The extreme case is where the carbonization
temperature is 200C, with maximum yield and lowest
fixed carbon content.
– This is sufficient to produce little more than a through
drying and light charring of the wood (low quality).
 FACTORS INFLUENCING THE
CHARCOAL YIELD
• Carbonization Temperature
– Effect of Carbonization Temperature on Yield and
Fixed Carbon Content of Charcoal
Carbonization Yield of charcoal as % of oven Fixed carbon as % of dry
Temperature C dry weight of original wood weight of charcoal
200 91.8 52.3
250 65.2 70.6
300 51.4 73.2
500 31.0 89.2
600 29.1 92.2
700 27.8 92.8
800 26.7 95.7
900 26.6 96.1
1000 26.3 96.6
1100 26.1 96.4
 FACTORS INFLUENCING THE
CHARCOAL YIELD
• Water Content
– The water content of the wood also affects the final
yield because it determines the proportion of the
charge which has to be burned during the drying
phase.
– For example, for green wood with a moisture content
of 56% on a wet basis, 17.4% of the original dry
weight of the wood is lost in driving off the water.
– If the wood is pre-dried to a moisture content of 17%,
then the proportion required to drive off the water
falls to 2.7%.
– This means that 14.3% of the original wood charge,
which would otherwise have been burned to drive off
the water, is available for turning into charcoal.
 FACTORS INFLUENCING THE
CHARCOAL YIELD
• Water Content
– High initial water content also reduces the maximum
temperature reached during carbonization.
– In addition, it extends the carbonization time.
– Therefore influence of moisture content on the final
yield is very complex.
– When charcoal with a high fixed carbon content is
required, the use of dry wood leads to a higher yield.
– It reduces the time needed for carbonization, which is
a particularly important factor when charcoal making
equipment with a high capital cost is being used.
– In such cases, it usually makes considerable
technical and economic sense to reduce the water
content of wood before making it into charcoal.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Classifications Systems for Carbonizing Wood

Internal source of heat to dry External source of heat to dry

and heat wood achieved by and heat wood, by burning
burning part of the charge wood, gas, coal or oil and tars

Indirect Direct heating by

Pits; Brick Metal heating recirculation of neutral
Mounds through hot gas through wood to
Kilns Kilns
retort walls be carbonized

Metal Brick Metal

Retorts Kilns Kilns

Fixed Portable Portable Fixed

 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Pits / Mounds
– Using earth as a shield against oxygen and to
insulate the carbonizing wood against excessive loss
of heat is the oldest system of carbonization.
– There are two distinct ways to use an earth barrier in
charcoal making:
✓ one is to excavate a pit, put in the charge of wood and cover
the pit with excavated earth to seal up the chamber.
✓ The other is to cover a mound or pile of wood on the ground
with earth.

– The earth forms the necessary gas-tight insulating

barrier behind which carbonization can take place
without leakage of air.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Pits
– A stratum of deep soil is needed for this method.
Figure shows a large pit of about 30 m³ gross volume.
It will hold a charge of about 26 m³.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Pits
– A sandy loam is preferred with adequate depth.
– The pit is loaded with logs measuring 2.4 m or less,
which will fit easily across the pit.
– To ensure that the wood is properly heated for
carbonization, the hot gas is allowed to pass along
the floor of the pit by placing the charge on a crib of
logs.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Pits
– Hot gases produced by partial burning of the wood
charged slowly dry out the earth and heat up the rest
of the wood to the carbonization point, about 280°C.
– Spontaneous decomposition of the wood, with
evolution of heat, then occurs to form charcoal.
Copious volumes of water vapour, acetic and other
acids, methanol and tars, are produced at the same
time.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Pits
– The carbonization stage may take 20 to 30 days to
complete and it is accompanied by a marked volume
reduction of the wood charge to 50-70% of its initial
volume.
– The earth covering the pit slowly sinks during the
carbonization and any cracks or holes which form
must be closed to prevent air leakage.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Pits
– Earth pit during burning
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Mounds
– Earth mound is an alternative to digging a pit, where
the wood is stacked above the ground and covered
with earth.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Mounds
– Essentially the process is the same as the pit - the
wood to be carbonized is enclosed behind an air-tight
well made from earth.
– The earth mound is preferred over the pit where the
soil is rocky, hard or shallow, or the water table is
close to the surface.
– By contrast the pit is ideal where the soil is well
drained, deep and loamy.
– The mound is also more practical in agricultural
zones where fuel wood sources may be scattered and
it is desirable to make the charcoal near a village or
other permanent site.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Mounds
– A mound site can be used over and over again,
whereas pits tend to be used a few times and then
new ones dug to follow the timber resource.
– The repeated digging of pits also disrupts cultivation
for crops or pasture.
– The fuel wood to be carbonized, in a mound can also
be gathered slowly over a period of months, stacked
in position and allowed to dry out well before
covering and burning.
– This fits in well with the life style of a small farmer
who may gather scrap wood, branches and logs and
stack them carefully to form the mound.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Mounds
– The typical village type charcoal burning mound is
about 4 m in diameter at the base and about 1 to 1.5
m high, approximately a flattened hemisphere.
– About six to ten air inlets are made at the base and an
opening at the top about 20 cm in diameter allows
exit of smoke during burning.
– All openings must be sealed with earth when burning
is complete and the mound is allowed to cool.
– A hybrid system containing elements of the earth
mound and the pit could also be used.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Mounds
– The above type of mound has been modified by
inserting a central chimney made of old oil drums
welded together.
– The chimney improves gas circulation which reduces
the amount of brands (partially carbonized wood
pieces) and speeds up the carbonization. Less
brands means an improved yield of charcoal.
– The mound is covered with grass and shrubs and
then sand or loam.
– The chimney is placed at the edge of the pile as in the
diagram, with its base opening connected to the base
of the pile.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Mounds
– This modified earth kiln, called a Casamance kiln, is
shown in the figure.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Mounds
– The charcoal iron industry of Sweden brought the
design and operation of large mound type kilns to a
high stage of perfection.
– The main improvements were the use of an external
chimney connected to a flue constructed beneath the
pile and adoption of a circular ground plan for the pile
which reduced heat loss during carbonization and
improved gas circulation.
– The bottom of the base is covered with logs forming a
grate or crib on which the wood is piled vertically.
– The grate forms a free space between the bottom and
the wood charge through which the air necessary for
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Mounds
– The piled wood is covered with leaves and grass and
then earth about 20 cm thick.
– The pile has an outside stack made of steel drums,
which is connected to the pile through a flue cut into
the ground, running under the pile and covered with
round loge.
– The pile has a number of air vents located around the
circular base.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Earth Mounds
– The Swedish earth kiln with chimney
 DIFFERENT TYPES OF
CHARCOAL KILN
• Brick Kilns
– Properly constructed and operated brick kilns are
one of the most effective methods of charcoal
production.
– They have proved themselves over decades of use to
be low in capital cost, moderate in labour
requirements and capable of giving good yields of
quality charcoal suitable for all industrial and
domestic uses.
– The ability of the brick kiln to conserve the heat of
carbonization is an important factor in its high
conversion efficiency of wood to charcoal.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Brick Kilns
– There are many designs of brick kilns in use
throughout the world.
– The designs of traditional brick kilns have been
refined over many hundreds of years but there are
other types of brick kiln in use which have been
subject in recent years to systematic experiment to
improve them.
✓ Brazilian beehive kilns,
✓ Argentine half-orange kiln,
✓ European Schwartz kiln
✓ Missouri kiln of the U.S.A.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Brick Kilns
– Argentine half orange or beehive brick kiln.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Brick Kilns
– Argentine half orange or beehive brick kiln.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Brick Kilns
– Brazilian beehive kiln.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Brick Kilns
– Brazilian beehive kiln.
 DIFFERENT TYPES OF
CHARCOAL KILN
• Metal Kilns