Pyrolysis Definition

What is Pyrolysis?
Pyrolysis can be defined as the process of subjecting substances to highly
elevated temperatures in relatively inert atmospheres in order to facilitate their thermal
decomposition. It is important to note that the process of pyrolysis brings about a chemical
change in the substance subjected to it (the chemical compositions of the initial reactant
feedstock and the final product are different). The term ‘pyrolysis’ has Greek roots and can be
roughly translated as “fire separating”. Generally, substances that are subjected to pyrolysis
undergo a chemical decomposition reaction and break down into multiple product compounds.
The process of pyrolysis is widely used to break down organic substances.
For example, the charring of wood (or the incomplete combustion of wood) that result in the
formation of charcoal involves the process of pyrolysis. Typically, the pyrolysis of an organic
substance will produce multiple volatile products and will also leave behind a solid residue
which is often highly enriched with carbon. It can be noted that extreme pyrolysis, which often
leaves only carbon as a residue, is commonly known as carbonization. It can also be noted that
pyrolysis is widely considered as the initial step for other related processes such as combustion
and gasification.
The chemical industry makes extensive use of the process of pyrolysis.
One of the most important applications of this process is in the production of ethylene and other
important carbon compounds from coal and petroleum. Furthermore, it can be noted that these
compounds can also be extracted from certain organic matter such as wood. Coke can be
obtained from coal (along with a wide spectrum of different compounds) via the process of
pyrolysis.
Process occurring in pyrolysis:
Pyrolysis generally consists in heating the material above
its decomposition temperature, breaking chemical bonds in its molecules. The fragments usually
become smaller molecules, but may combine to produce residues with larger molecular mass,
even amorphous covalent solids.
In many settings, some amounts of oxygen, water, or other
substances may be present, so that combustion, hydrolysis, or other chemical processes may
occur besides pyrolysis proper. Sometimes those chemical are added intentionally, as in the
burning of firewood, in the traditional manufacture of charcoal, and in the steam cracking of
crude oil.
Conversely, the starting material may be heated in a vacuum or in
an inert atmosphere to avoid adverse chemical reactions. Pyrolysis in a vacuum also lowers
the boiling point of the byproducts, improving their recovery.
When organic matter is heated at increasing temperatures in open containers, the following
processes generally occur, in successive or overlapping stages:
 Below about 100 °C, volatiles, including some water, evaporate. Heat-sensitive
substances, such as vitamin C and proteins, may partially change or decompose already at
this stage.
 At about 100 °C or slightly higher, any remaining water that is merely absorbed in the
material is driven off. Water trapped in crystal structure of hydrates may come off at
somewhat higher temperatures. This process consumes a lot of energy, so the temperature
may stop rising until this stage is complete.
 Some solid substances, like fats, waxes, and sugars, may melt and separate.
 Between 100 and 500 °C, many common organic molecules break down.
Most sugars start decomposing at 160–180 °C. Cellulose, a major component of
wood, paper, and cotton fabrics, decomposes at about 350°C.Lignin, another major wood
component, starts decomposing at about 350 °C, but continues releasing volatile products up
to 500 °C. The decomposition products usually include water, carbon
monoxide CO and/or carbon dioxide CO
2, as well as a large number of organic compounds. Gases and volatile products leave the
sample, and some of them may condense again as smoke. Generally, this process also
absorbs energy. Some volatiles may ignite and burn, creating a visible flame. The non-
volatile residues typically become richer in carbon and form large disordered molecules,
with colors ranging between brown and black. At this point the matter is said to have been
"charred" or "carbonized".
 At 200–300 °C, if oxygen has not been excluded, the carbonaceous residue may start to
burn, in a highly exothermic reaction, often with no or little visible flame. Once carbon
combustion starts, the temperature rises spontaneously, turning the residue into a
glowing ember and releasing carbon dioxide and/or monoxide. At this stage, some of
the nitrogen still remaining in the residue may be oxidized into nitrogen oxides like NO
2 and N2O
3. Sulfur and other elements like chlorine and arsenic may be oxidized and volatilized at this
stage.
 Once combustion of the carbonaceous residue is complete, a powdery or solid mineral
residue (ash) is often left behind, consisting of inorganic oxidized materials of high melting
point. Some of the ash may have left during combustion, entrained by the gases as fly
ash or particulate emissions.

What Happens to the Feedstock During Pyrolysis?

 The feedstock that is subjected to pyrolysis is exposed to temperatures above its

decomposition temperature. At this point, the chemical bonds that hold the molecules of
the feedstock together are broken. This results in the fragmentation of the molecules of
the feedstock into smaller molecules. It is not uncommon for these smaller molecules to
participate in chemical reactions with each other to form other larger molecules within
the pyrolysis setup. In fact, some of these molecules even go on to form covalently
bonded amorphous solids.
 In most cases, the process of pyrolysis is carried out in the absence of oxygen and water.
This is done to make the atmosphere as inert as possible. However, in some cases, a very
small quantity of water and oxygen is allowed to enter the pyrolysis setup. This is done in
 order to facilitate other important processes such as combustion and hydrolysis (which
can play a role in altering the types of products that are obtained from the pyrolysis of the
feedstock). Furthermore, certain chemical substances may also be mixed with the
feedstock in order to obtain specific products from the pyrolysis process. Common
examples of such practices can be observed in the steam cracking of crude oil and the
production of charcoal from the pyrolysis of firewood.
 When some organic feedstock is subjected to pyrolysis, the following processes are
known to take place.
 When the temperature of the environment is below 100 degrees Celsius, certain volatile
compounds in the feedstock mixture (such as water) undergo evaporation. Furthermore,
the components of the feedstock that are sensitive to heat (such as proteins and vitamin C
or ascorbic acid) undergo partial changes in their chemical compositions. It is not
uncommon for these proteins and vitamins to begin going through the decomposition
process at this stage.
 When the temperature of the environment crosses the 100 degrees Celsius mark, all
remaining traces of water that was absorbed by the feedstock are removed. However, the
water that is trapped inside hydrated crystals may still require higher temperatures to
break free and evaporate. A lot of energy is absorbed by the feedstock at this point in
order to convert all the liquid water into water vapour. At this temperature point, the
sugars, fats, and waxes that are present in the organic feedstock may undergo melting and
separate from the feedstock.
 In the temperature range that lies between 100 degrees Celsius and 500 degrees Celsius,
most of the common organic molecules that are present in the organic feedstock undergo
a decomposition reaction and break down into smaller molecules. For sugars, the ideal
temperature range under these conditions for a decomposition reaction lies in between
160 degrees Celsius and 180 degrees Celsius. If there is any cellulose present in the
feedstock, it will undergo decomposition when the temperature of the environment
reaches 350 degrees Celsius. Another common compound that begins to undergo
decomposition at such temperatures is lignin – a vital component of wood. However,
lignin is known to continue releasing volatile products during pyrolysis processes up to
temperatures of 500 degrees Celsius. Other notable products of this decomposition
reaction include carbon dioxide, carbon monoxide, and water.
 Once the combustion of all the carbonaceous residues are finally completed, the product
left behind is a powdery substance which is usually referred to as ash. This ash is known
to be made up of inorganic materials that are oxidized. These inorganic substances have
very high melting points, which is the reason why they retain their solid nature despite
the extreme temperatures that they had to endure during the pyrolysis process. It is
important to note that in the scenario where certain metals were present in the initial
organic feedstock subjected to pyrolysis, then the metals are usually concentrated in the
ash in the form of metal oxides or metal carbonates.
Figure 2.

Simplified flow diagram for typical pyrolysis unit. (a) Biochar and bio‐oil production. (b)
Biochar and heat production.

figure  1.
Biomass conversion process to obtain value‐added products.

Types of Pyrolysis:
 Fast pyrolysis:

During the fast pyrolysis process, biomass residues are

heated in absence of oxygen at high temperature using higher heating rate. Based on the initial
weight of the biomass, fast pyrolysis can provide 60–75% of liquid biofuels with 15–25% of
Biochar residues. It can also yield 10–20% of gaseous phase depending on the biomass used. The
process is characterized by small vapour retention time. However, quick chilling of vapours and
aerosol can ensure higher bio‐oil yield. It can provide liquid biofuels for turbine, boiler, engine,
power supplies for industrial applications. Fast pyrolysis technology is getting implausible
acceptance for producing liquid fuels due to certain technical advantages

 It can ensure preliminary disintegration of the simple oligomer and lignin portions from
lignocellulosic biomass with successive upgrading.
 2. The scaling up of this process is economically feasible
 3. It can utilize second generation bio‐oil feed stocks such as forest residues, municipal
and industrial wastes.
 4. It provides easy storability and transportability of liquid fuels.
 5. It can ensure secondary transformation of motor fuels, additives or special chemicals.
Flash pyrolysis:
The flash pyrolysis process of biomass can give solid, liquid and gaseous
products. The bio‐oil production can go up to 75% using flash pyrolysis. This procedure is
carried out by speedy devolatilization under inert atmosphere using higher heating rate with high
pyrolysis temperatures around 450 and 1000°C. In this process, the gas residence time (less than
1 s) is too little. Nevertheless, this process has poor thermal stability. Due to catalytic effect of
the char, the oil becomes viscous and sometimes it contains some solid residues also.
Slow pyrolysis:
Slow pyrolysis can yield good quality charcoal using low temperature and low
heating rates. The vapour residence time can be around 5–30 min in this process. The volatile
organic fractions present in vapour phase continue to react with each other to yield char and
some liquid fractions [61]. The quality of bio‐oil produce in this process is very low. Longer
residence time initiates further cracking to reduce the yield of bio‐oil. The process suffers from
low heat transfer values with longer retention time leading to enhance the expenditure by higher
input of energy.


Pyrolytic Products

Biochar

Biochar is solid amorphous carbonaceous materials obtained from thermal

degradation of lignin and hemicelluloses polymer during the pyrolysis process. The
physiochemical properties of Biochar matrix greatly vary with reactor type and design, biomass
composition, particle size and extent of drying, chemical activation, heating rate, reaction time,
pressure, flow rate of inert gas, etc. If higher heating rate up to 105–500°C/s is used for less
retention time and finer particle size, finer Biochar is produced during fast pyrolysis process,
whereas larger particle‐sized feedstock during slow pyrolysis results in a coarser Biochar.
Usually woody biomass results in coarser Biochar whereas crop residues and manures yield
more fragile‐structured Biochar. Earlier investigation demonstrated that Biochar yield varies for
different temperature regions in a fluidized bed pyrolysis reactor. The results showed that at a
low temperature of around 450–500°C, the yield of Biochar was high as the rate of
devolatilization was low. At a temperature around 550–650°C, the yield of Biochar was
decreased. At that temperature maximum yield achieved was about 8–10%. However at higher
temperature, around 650°C, Biochar yield was very low. Biochar predominantly contains larger
portion of fixed carbon along with moisture, volatile materials, hydrogen and various other
constituents in two structures: stacked crystalline Graphene sheets and randomly ordered
amorphous aromatic structures. The aromatic portion of Biochar contains H, O, N, P and S.
These inorganic species have a pronounced impact on the physical and chemical properties of a
Biochar. The percentages of these constituents depend on the type of biomass and the process of
the pyrolysis process. Biochar can be utilized as solid fuel in boilers. After catalytic pre‐
treatment, it can be used to produce activated carbon, carbon nanotubes and gaseous fractions,
etc.

Syngas

Based on biomass composition and process parameters of pyrolysis, the composition of Syngas
varies. Usually gaseous products obtained after pyrolysis mostly comprises of H2 and CO. It also
contains negligible fraction of CO2, N2, H2O, mixture of alkanes, alkenes and alkynes, such as
CH4, C2H4, C2H6, tar, ash, etc. Higher pyrolysis temperature leads to endothermic reaction. With
the increase of pyrolysis, the vaporization of moisture from the biomass takes place initially.
After that, thermal degradation and devolatilization take place. At this stage, tar is produced and
volatile species are released. A series of secondary reactions such as decarboxylation,
decarbonylation, dehydrogenation, deoxygenation and cracking takes place to produce mixture
of Syngas. Therefore, higher temperature initiates the tar decomposition, which results in the
production of Syngas with decreased yield of oil and char. For a given temperature, dry biomass
yields the highest amount of gas at the early stage of pyrolysis, whereas with wet biomass the
production of the maximum quantity happens later in the process. This is evident and expected as
increase in humidity results in increase in drying time. The cracking of hydrocarbon produces
hydrogen at higher temperature. Due to presence of oxygen in biomass, CO and CO2 are
produced. The presence of oxygenated polymer that is cellulose determines the evolution of
carbonated oxides produced. The lighter hydrocarbons such as CH4, C2H4, C2H6, etc. are formed
due to reforming and cracking of heavier hydrocarbons and tar in the vapour phase. Plasma
reactor using radio frequency can produce up to 76.64% Syngas. The advantages of using Syngas
are that it produces a considerably minor quantity of unburnt hydrocarbon (HC) and carbon
monoxide (CO) with higher emissions of nitrogen oxides (NOx). It is reported that, CO and H2 in
Syngas have comparatively elevated flame speed and temperature which produce greater
temperatures in engines to increase the speed of production of CO2and NOx. Slow pyrolysis
processes give about 10–35% of biogas. At higher temperature flash pyrolysis gives more
Syngas. Calcined dolomite was used at 750–900°C as a catalyst using fixed bed reactor to
produce Syngas.

Bio‐oil:

The oil extracted after pyrolysis is a mixture of about 300–400 compounds. The oil
obtained after pyrolysis has tendency to become viscous due to ageing as numerous physical and
chemical changes with subsequent loss of volatile matters take place. However, the ageing
process can be slowed down by storing them in cool places. Previously it was found that energy
crops can yield oil with high ash/metal content and water. The presence of water will lower the
heating values as well as it will make the phase separation difficult. Thus for commercial
application, presence of ash and lignin inside the biomass substrate should be carefully
monitored. Earlier thermal efficiency of the pyrolysis oils was compared with diesel, but they
demonstrated unwarranted delay in ignition. On the other hand, the quantity, quality and
constancy of pyrolysis oil can also be improved by method variables such as heating rate,
temperature and retention times. Type of different reactors (ablative and fixed), particle size and
char accretion can disturb the amount and feature of the pyrolysis oil. Till currently, there is no
inclusive research to diminish these things. Therefore, additional research is obligatory in order
to achieve a complete representation of thermo chemical transformation processes to yield
superior quality pyrolysis oil. Bio‐oil which should be used commercially should preserve its
chemical and physical properties such as constancy and viscosity. If the oil contains low
molecular weight compound, it is possible. The oil contains high molecular weight compounds if
the starting biomass contains larger proportion of lignin.

Advantages of Pyrolysis:
What are the Advantages of Pyrolysis?

The key benefits of pyrolysis include the following:

 It is a simple, inexpensive technology for processing a wide variety of feedstocks.

 It reduces waste going to landfill and greenhouse gas emissions.
 It reduces the risk of water pollution.
 It has the potential to reduce the country’s dependence on imported energy resources by
generating energy from domestic resources.
 Waste management with the help of modern pyrolysis technology is inexpensive than
disposal to landfills.
  The construction of a pyrolysis power plant is a relatively rapid process.
 It creates several new jobs for low-income people based on the quantities of waste
generated in the region, which in turn provides public health benefits through waste
cleanup.

Application of Pyrolysis

Some of the major applications of pyrolysis include the following:

 It is widely used in the chemical industry to produce methanol, activated carbon, charcoal
and other substances from wood.
 Synthetic gas produced from the conversion of waste using pyrolysis can be used in gas
or steam turbines for producing electricity.
 A mixture of stone, soil, ceramics, and glass obtained from pyrolytic waste can be used as
a building material - construction slag or for filling landfill cover liners.
 It plays a major role in carbon-14 dating and mass spectrometry.
 It is also used for several cooking procedures like caramelizing, grilling, frying, and
baking.

Applications of Pyrolysis in Forensic Analysis:

 Forensic chemists apply the tools of analytical chemistry for the extraction, isolation and
analysis of the target compounds that characterize ignitable liquid residues (ILR) in arson
case.
 Pyrolysis (Py)-GC/MS appears as valuable very informative analytical technique of car
paint samples examination for examination in different hit and run cases.
 One use of Pyrolysis Gas Chromatography (PGC) is in the characterization of drugs. As
drug contains organic mixtures in different ratios so they can easily be classified and
identify.
 Laser micro-pyrolysis gas chromatography-mass spectrometry is used for the analysis of
paint, photocopier toner, and synthetic fiber materials to test the forensic potential of this
emerging technology.