PYROLYSIS

PRESENTATION BY- T.GOPINADH

DEFINITION OF PYROLYSIS ..

 Pyrolysis can be defined as the “direct thermal decomposition of the organic

components” in carbonaceous material , in the absence of oxygen to yield an array of
useful products –liquid and solid derivatives and fuel gases.
 Pyrolysis processes were utilized for the commercial production of a wide range of fuels,
solvents, chemicals, and other products from biomass feedstocks.
 During pyrolysis, large complex hydrocarbon molecules of carbonaceous material
breakdown into relatively smaller and similar molecules of gas, liquid and char.
PURPOSE OF PYROLYSIS..

• Pyrolysis is one of the technology available to convert carbonaceous material to an

intermediate liquid product, that can be reused to drop the oxygenated fuel additives and
petrochemicals replacements.
• Used in production of chemical feedstock.
• Used in Energy conversion
• To find out the gas compositions of CO,H2 from the sample provided.
• To know the CV (Calorific value) ,ASH Percentage present in the sample.
PYROLYSIS PRODUCTS..

Pyrolysis involves a breakdown of large complex

molecules into several smaller molecules. Its product is
classified into three principal types:-

1. Liquid (tars, heavier

hydrocarbons, and water)

2. Solid (mostly char or

carbon)

3. Gas (e.g., CO2, H2O, CO,

C2H2, C2H4, C2H6, C6H6).
PYROLYSIS PRODUCTS (CONTD)..
LIQUID..

 The liquid yield, known as tar, bio-oil, or biocrude, is a black tarry fluid

containing up to 20% water.

It consists mainly of homologous phenolic compounds. Bio-oil is a mixture of

complex hydrocarbons with large amounts of oxygen and water.

PYROLYSIS PRODUCTS (CONTD)..
SOLID..

 Biochar is the solid yield of pyrolysis. It is primarily carbon

(~85%), but it can also contain some oxygen and hydrogen

Unlike fossil fuels, biomass contains very little inorganic ash.

PYROLYSIS PRODUCTS (CONTD)..
GAS..
 Primary decomposition of biomass produces both condensable gases (vapor) and non
condensable gases (primary gas).
 The vapors, which are made of heavier molecules, condense upon cooling, adding to the
liquid yield of pyrolysis.
 The noncondensable gas mixture contains lower-molecular-weight gases like carbon
dioxide, carbon monoxide, methane, ethane, and ethylene.
BEHAVIOR OF BIOMASS AT DIFF TEMP..
BEHAVIOR OF BIOMASS AT DIFF TEMP..
BEHAVIOR OF BIOMASS AT DIFF TEMP..
CLASSIFICATION OF PYROLYSIS..

Conventional /Slow pyrolysis----- used to modify the

solid materials ,minimizing the oil produced.

Fast pyrolysis-----It maximizes the gases and oil

produced.
Ultra-fast / flash pyrolysis------This is an extremely
rapid thermal decomposition method with a high
heating rate.
CLASSIFICATION OF PYROLYSIS (CONTD..)

Method Temp (degC) Residence Heating rate Major

time (deg C/S) Products

Conventional / Med-High Long Low Gases, char,

Slow pyrolysis 400-500 5-30 min 10 tar.

Fast pyrolysis Med-High Short High Bio-oil

400-650 0.5-2 sec 100

Ultra fast High Very short Very high Gases, Bio-oil,

/flash pyrolysis 700-1000 < 0.5 sec > 500 Chemicals
 SLOW PYROLYSIS..
 Carbonization is a slow pyrolysis process, in
which the production of char coal or char is the
primary goal. It is the oldest form of pyrolysis,
which is in use for thousands of years.
 The biomass is heated slowly in the absence of
oxygen to a relatively low temperature (~400C)
over an extended period of time, which in ancient
times ran for several days to maximize the char
formation.
SLOW PYROLYSIS..

 A typical beehive oven in which large logs were stacked and covered by a clay wall. It
allows a certain amount of oxygen for partial combustion of wood.
 A small fire at the bottom provided the required heat for carbonization. The fire
essentially stayed in the well-insulated closed chamber
 Carbonization allows adequate time for the condensable vapor to be converted into char
and non condensable gases.
 Conventional pyrolysis involves all three types of pyrolysis product (gas, liquid, and
char). As such, it heats the biomass at a moderate rate to a moderate temperature (~600C).
The product residence time is on the order of minutes.
FAST PYROLYSIS..

 The primary goal of fast pyrolysis is to maximize the production of liquid or bio-oil.
 The biomass is heated so rapidly that it reaches the peak (pyrolysis) temperature before it
decomposes.
 The heating rate can be as high as 1000-10,000°C/s, but the peak temperature should be
below 650°C if bio-oil is the product of interest. However, the peak temperature can be
up to 1000°C if the production of gas is of primary interest.
 Fluidized beds are used for fast pyrolysis.
FLASH PYROLYSIS..

 In flash pyrolysis, biomass is heated rapidly in the absence of oxygen to a relatively

modest temperature range of 450-600°C.
 The product, containing condensable and non condensable gas, leaves the pyrolyzer
within a short residence time of 30-1500 ms.
 Upon cooling, the condensable vapor is then condensed into a liquid fuel known as “bio-
oil.” Such an operation increases the liquid yield while reducing the char production. A
typical yield of bio-oil in flash pyrolysis is 70-75% of the total pyrolysis product.
PYROLYSIS PROCESS ..
SAMPLE DATA..

Sample Name Rubber Wood Sample Name Rubber Wood

Sample size 4 to 5 mm Top packing Steel mesh packing

Sample Top packing

570 gm 1.6 kg
weight/quantity quantity
Top packing bed
Sample bed height 180 gm 330 mm
height
Steel mesh Top free space 80 mm
Bottom packing
packing
Top retarder face to
Bottom packing 200 mm
600 gm furnace surface
quantity Total depth of the
Bottom packing bed 920 mm
130 mm retarder
height
EXPERIMENTAL SET UP..
• Firstly we have to fill the material in the retarder and also we have to give
the proper pipe connections.
• After completion of all the setup ,we have to conduct the leak test(To find
the issues)
• If, no issues found after the completion of leak test bubbles formed in the
three bubbler jars.
EXPERIMENTAL PROCESS..
PYROLYSIS PROCESS (CONTD)…

Firstly, we have to give the heat to furnace, starting the temp range from
100 degC.
Then we will observe the temp values of retord reactor and furnace in the
control panel as T1and T2.
Then, the heat is increased slowly, we have to note down the values of
T1,T2 and S.P(Set Point Temp) in the log book.
EXPERIMENTAL PROCESS..
PYROLYSIS PROCESS (CONTD)…

 We are giving the pure nitrogen gas to retorder ,in this pyrolysis will be occurred with the presence
of heat through the heating element.
 In the reactor there is a multi-stage packings such as, steel mesh sample, Bío-mass sample.
 After, we are controlling the pyrolysis temp with the help of PID temp then, we will notice that the
gas will come into the bubbler. And we can see the bubbles will form in the bubbler. Then, we will
confirm that the gas is passing through the lines.
 Then, we are analyzing the composition of gas through the online gas analyzer name as GC(Gas
Chromatography).
 To, analyze the gas we have to maintain the flow rate of 1.5 l/min, and we are using the the nitrogen
gas to maintain the mentioned flow rate.
ADVANTAGES AND DIS-ADVANTAGES OF
PYROLYSIS..
• It prevents hazardous waste from reaching landfills.
• It has no emission of toxic gases
• Syngas from biomass can be used to generate electric and thermal energy.
• It requires high operational and investment costs.
• Air purification is necessary to treat flue gases from the pyrolysis.
TYPES OF PYROLYSIS.

Fixed or moving bed

Bubbling fluidized bed

Circulating fluidized bed
(CFB)
Ultra rapid reactor

Rotating cone

Ablative reactor

Vacuum reactor
TYPES OF PYROLYSIS..
FIXED BED..
 This is a very simple technology that gives
priority to the production of bio-oils, which are
relatively uniform in size with low fines
content.
 Its is made up of two basic components, that is
the gas cooling compartment, and the cleaning
system by filtering through cyclone, wet
scrubbers, and dry filters.
TYPES OF PYROLYSIS..
FIXED BED (CONTD)..
During reaction, the solid sample is allowed to pass through a vertical
shaft, where it encounters an upwardly moving counter current gas stream
product.
This reactor can be made with either steel, firebricks, or concrete.
The reactor which has its priority for applications involving small-scale
heat and power.
TYPES OF PYROLYSIS..
BUBBLING FLUIDIZED BED..
 The biomass is heated in an environment devoid
of oxygen and decomposed into gas, vapour ,
aerosols, and char and these components are
finally collected from the reactor.
 While the charcoal is collected using the cyclone
separator and stored, the vapour is cooled rapidly
and condensed into high quality bio-oil and stored
with about 70% yield of biomass weight (dry
weight).
TYPES OF PYROLYSIS..
CFD BED REACTOR..
 The features of this reactor is similar to that
of a bubbling fluidized bed reactor
described earlier expect the fact that the
residence time for the vapours and char is
shorter.
 This make the gas velocity and the content
of char in the bio-oil to be higher.
ADVANTAGES AND DIS-ADVANTAGES OF
PYROLYSIS REACTORS.
ADVANTAGES AND DIS-ADVANTAGES OF
PYROLYSIS REACTORS (CONTD)..
PRODUCTION OF LIQUID THROUGH
PYROLYSIS…
• Pyrolysis is one of several means of production of liquid fuel from biomass
• The maximum yield of organic liquid (pyrolytic oil or bio-oil) from thermal decomposition may be
increased to as high as 70% (dry weight) if the biomass is rapidly heated to an intermediate
temperature and if a short residence time in the pyrolysis zone is allowed to reduce secondary
reactions.
• A slower heating rate, a lower temperature, and a longer residence time maximize the yield of solid
char.
• A higher heating rate, a higher temperature, and a shorter residence time maximize the gas yield.
• A higher heating rate, an intermediate temperature, and a shorter residence time maximize the
liquid yield.
PYROLYSIS PRODUCT YIELD..

The product of pyrolysis depends upon the

design of pyrolizer, the physical and
chemical characteristics of the bio-mass,
and important operations parameters such
as,
• Heating rate
• Final temp rate (Pyrolysis temp)
• Residence time in the reaction zone
PYROLYSIS PRODUCT YIELD (CONTD)..

 Besides these, the tar and the yields of other products depend on (i) pressure, (ii) ambient
gas composition, and (iii) presence of mineral catalysts.
 By changing the final temperature and the heating rate, it is possible to change the
relative yields of the solid, liquid, and gaseous products of pyrolysis.
 Heating yields higher volatiles and more reactive char than those produced by a slower
heating process; slower heating rate and longer residence time result in secondary char
produced from a reaction between the primary char and the volatiles
PYROLYSIS PRODUCT YIELD (CONTD)..
EFFECT OF PYROLYSIS TEMP..
 During pyrolysis, a fuel particle is heated at a defined rate from the
ambient to a maximum temperature, known as the pyrolysis
temperature.
 The fuel is held there until completion of the process. The pyrolysis
temperature affects both composition and yield of the product.
 The amount of char produced also depends on the pyrolysis
temperature. Low temperatures result in greater amount of char; high
temperatures result in less.
PYROLYSIS PRODUCT YIELD (CONTD)..
EFFECT OF PYROLYSIS TEMP..
 The Fig shows how the amount of solid
char produced from the pyrolysis of a
grape bagasse decreases with increasing
temperature, but the heating value of the
char increases with temperature.
 This happens because the fixed carbon,
which has a higher heating value, in the
char increases while the volatile content
of the char decreases.
PYROLYSIS PRODUCT YIELD (CONTD)..
EFFECT OF HEATING RATE..
 The rate of heating of the biomass particles has an important influence on the yield and
composition of the product.
 Rapid heating to a moderate temperature (400-600°C) yields higher condensable volatiles
and hence more liquid, while slower heating to that temperature produces more char.
 During slow heating, a slow or gradual removal of volatiles from the reactor permits a
secondary reaction to occur between char particles and volatiles, leading to a secondary
char formation
PYROLYSIS PRODUCT YIELD (CONTD)..
EFFECT OF HEATING RATE..
A To maximize char production, use a slow heating rate (<0.01-
2.0°C/s), a low final temperature, and a long gas residence time.
B To maximize liquid yield, use a high heating rate, a moderate final
temperature (450-600°C), and a short gas residence time.
C To maximize gas production, use a moderate to slow heating rate, a
high final temperature (700-900°C), and a long gas residence time.

Production of charcoal through carbonization uses step (a). Fast pyrolysis uses step (b) to
maximize liquid yield. Step (c) is used when gas production is to be maximized
PYROLYSIS KINETICS

 A study of pyrolysis kinetics provides important information for the engineering design
of a pyrolyzer or a gasifier.
 It also helps explain how different processes in a pyrolyzer affect product yields and
composition.
 Three major processes that influence the pyrolysis rate are chemical kinetics, heat
transfer, and mass transfer.
 Let us discuss, about the physical and chemical aspects that govern the process
PYROLYSIS KINETICS (CONTD)..
PHYSICAL ASPECTS..
 From a thermal standpoint, we may divide the pyrolysis process into four stages. Although
divided by temperature, the boundaries between them are not sharp; there is always some
overlap:-
 1. Drying (~100°C). During the initial phase of biomass heating at low temperature, the free
moisture and some loosely bound water is released. The free moisture evaporates, and the
heat is then conducted into the biomass interior.
 If the humidity is high, the bound water aids the melting of the lignitic fraction, which
solidifies on subsequent cooling. This phenomenon is used in steam bending of wood,
which is a popular practice for shaping it for furniture
PYROLYSIS KINETICS (CONTD)..
PHYSICAL ASPECTS..
 2. Initial stage (100°-300°C). In this stage, exothermic dehydration of the biomass takes
place with the release of water and low-molecular-weight gases like CO and CO2.
 3. Intermediate stage (>200°C). This is primary pyrolysis, and it takes place in the
temperature range of 200-600°C. Most of the vapor or precursor to bio-oil is produced at
this stage. Large molecules of biomass particles decompose into char (primary char),
condensable gases (vapors and precursors of the liquid yield), and non condensable gases.
PYROLYSIS KINETICS (CONTD)..
PHYSICAL ASPECTS..
 4. Final stage (~300-900°C). The final stage of pyrolysis involves secondary cracking of
volatiles into char and non condensable gases. If they reside in the biomass long enough,
relatively large-molecular-weight condensable gases can crack, yielding additional char
(called secondary char) and gases.
 This stage typically occurs above 300°C (Reed, 2002, p. III-6). The con densable gases,
if removed quickly from the reaction site, condense outside in the downstream reactor as
tar or bio-oil.
 Temperature has a major influence on the product of pyrolysis. The carbon dioxide yield
is high at lower temperatures and decreases at higher temperatures. The release of
hydrocarbon gases peaks at around 450°C and then starts decreasing above 500°C,
boosting the generation of hydrogen.
HEAT TRANSFER IN A PYROLYZER

 During pyrolysis, heat is transported to the particle’s outer surface by radiation and
convection. Thereafter, it is transferred to the interior of the particle by conduction and
pore convection.
 The following modes of heat transfer are involved in this process,
 Conduction inside the particle
 Convection inside the particle pores
 Convection and radiation from the particle surface.
MASS TRANSFER IN A PYROLYZER

Mass transfer can influence the pyrolysis product. For example,

a sweep of gas over the fuel quickly removes the products from
the pyrolysis environment. Thus, secondary reactions such as
thermal cracking, repolymerization, and re condensation are
minimized
EFFECT OF OPERATING VARIABLES ON THE
PYROLYSIS YIELD..
To Maximize Maximum Heating Rate Gas Residence
yield of Temperature Time

Char Low Slow Long

Liquid Low (~500°C) High Short

Gas High Low Long

BIO CHAR..

• Charcoal, also known as biochar, is a preferred product of slow pyrolysis at a moderate

temperature.
• Benefits of bio char..
• Reduces nutrient losses in soils
• Reduces fertilizer use
• Enhances marginal soil productivity
• Carbon negative emission
QUALITY OF BIO-CHAR..

 The quality of biochar is defined by its following characteristics:-

 The BET or internal surface area
 pH of the char
 Carbon recovery in char.
RESULTS AFTER PYROLYSIS..

Solid char sample weight 142 g

Liquid sample quantity 200 ml

THE END