Unit 2

1. What are the different types of pyrolysis process? Compare the different types of pyrolysis
process.
Pyrolysis is a process of chemically decomposing organic materials at elevated temperatures in the
absence of oxygen. The process typically occurs at temperatures above 430°C (800°F) and under
pressure.
The products of biomass pyrolysis include biochar, bio-oil and gases including methane, hydrogen,
carbon monoxide, and carbon dioxide.
In general, pyrolysis of organic substances produces volatile products and leaves a solid residue
enriched in carbon, char. The process is used heavily in the chemical industry, for example, to produce
ethylene, many forms of carbon, and other chemicals from petroleum, coal, and even wood, to produce
coke from coal.

There are four types of pyrolysis methods. The pyrolytic reactions differentiated by the
processing time and temperature of the biomass.
1) Conventional/slow pyrolysis
2) Fast pyrolysis and
3) Ultra-fast/flash pyrolysis.
4) Intermediate
Slow pyrolysis is typically used to modify the solid material, minimizing the oil produced.
Fast pyrolysis and ultra-fast (flash) pyrolysis maximize the gases and oil produced. Fast
pyrolysis is a rapid thermal decomposition of carbonaceous materials in the absence of oxygen
in moderate to high heating rates. It is the most common of the methods, both in research and
in practical use. The major product is bio-oil.
Ultra-fast or flash pyrolysis is an extremely rapid thermal decomposition pyrolysis, with a
high heating rate. The main products are gases and bio-oil.
Intermediate Pyrolysis
Intermediate pyrolysis processes typically involve reaction temperatures in the region of 400–
500 °C, comparatively slow heating rates of between 1 and 1000°C/s, and intermediate
feedstock residence times (e.g., ∼5–10min). This methodology is suitable for a diverse range
of feedstocks including waste wood and food, and even sewage sludge
2. Write the various process of pyrolysis – briefly.
Slow Pyrolysis

The pyrolysis of biomass undertaken with a heating rate of less than approximately 10°C/min
has long been used for the production of charcoal from wood, and is classified as a slow
pyrolysis process. Here, the biomass is heated to ∼500°C with reaction vessel residence times
for the resulting vapors being of the order of several hours, something that facilitates secondary
reactions between low molecular weight (volatile) components and gives rise to high charcoal
contents and lower liquid yields.

Intermediate Pyrolysis

Intermediate pyrolysis processes typically involve reaction temperatures in the region of 400–
500 °C, comparatively slow heating rates of between 1 and 1000°C/s, and intermediate
feedstock residence times (e.g., ∼5–10min). This methodology is suitable for a diverse range
of feedstocks including waste wood and food, and even sewage sludge. The solid residue (or
biochar) produced during the pyrolysis process can be used as an agricultural fertilizer
(something that provides a good example of a carbon sequestration cycle) or can be used to
produce energy through co-combustion in thermal power plants
Fast Pyrolysis

Fast pyrolysis is a process in which biomass is rapidly heated to high temperatures in the
absence of air (specifically oxygen). It occurs in a high-temperature range of 425–650°C at a
faster heating rate of 10–200°C/s, with a short solid resistance time of 0.5–10 s and with fine
particle size (< 1 mm) feedstock. In the fast pyrolytic process, biomass decomposes to generate
vapors, aerosol, and some charcoal like char. After cooling and condensation of vapors and
aerosol, dark brown liquid oil is formed. Fast pyrolysis is recommended when the desired
output is mainly liquid and gaseous products. Fast pyrolytic processes produce 60–75 wt% of
liquid bio-oil, 15–25 wt% of solid char, and 10–20 wt% of noncondensable gases, depending
on the feedstock used.

Flash Pyrolysis

Flash pyrolysis (sometimes called very fast pyrolysis), characterized by rapid heating rates
(>1000°C/s) and high reaction temperatures (900–1300°C), has been shown to afford high
yields of bio-oil with low resulting water content and conversion efficiencies of up to 70%.
The residence times used are even shorter than those of fast pyrolysis, typically less than 0.5s.
To obtain such high heating and heat transfer rates, the biomass feedstock particle size must be
as small as is practically possible, usually around 105–250μm (60–140 mesh size).

3. What are the different types of pyrolyzers?

Pyrolyzers have been used since ancient times to produce charcoal. Early pyrolyzers operated
in batch mode using a very slow rate of heating for long periods to maximize the production of
char. If the objective of pyrolysis is to produce the maximum amount of liquid or gas, then the
rate of heating, the peak pyrolysis temperature, and the duration of pyrolysis has to be chosen
differently. Table lists the choice of heating rate, temperature, and gas residence time for
maximization of the yield.
The choice of these operating parameters could influence the choice of reactor type. Several
types of reactors have been developed for pyrolysis. Based on the gas–solid contacting mode
in the reactor, they can be broadly classified as fixed bed, fluidized bed, and entrained bed, and
then further subdivided depending on design configuration. The following are some of the
major pyrolyzer designs in use:
1. Fixed bed

2. Bubbling fluidized bed

3. Circulating fluidized bed (CFB)

4. Ultrarapid reactor
5. Ablative reactor

6. Rotating cone

7. Vacuum reactor

8. Solar pyrolysis
4. Write down the short notes on charcoal.
Charcoal is an organic carbon compound. charcoal is produced by the incomplete combustion
of plant and animal products. Charcoal is widely used in outdoor cooking. Charcoal is generally
obtained from the burning of plant parts like wood, peat, bones, and cellulose. It is a highly
porous microcrystalline structure. Charcoal is mixed with clay to save energy in the brick
formation process. It is also known as impure graphite form. Charcoal has a porous texture and
a negative electrical charge. When charcoal is obtained from the coal, it is called activated coal.
Structure of Charcoal
Charcoal exists in many different forms. It exists in the impure form as the microcrystalline
graphitic form.
The charcoal structure shows it consists of an aromatic structure or carbon (carbon ring with
alternate double and single bond). This aromatic structure of charcoal consists of oxygen and
carbon-free radicals.
Properties of Charcoal
The properties of Charcoal are given below:

Physical Properties of Charcoal

 Charcoal exists in a solid amorphous state.
 The colour of the charcoal powder is black.
 Charcoal is a black porous solid that consists of carbon.
 It is a low-density compound.

 Charcoal shows low mechanical strength properties.

 The structure of carbon charcoal shows a large surface area.
 Charcoal acts as a good absorbent. It readily absorbs moisture.
 The high surface area of charcoal and high porosity enhances the contamination of
charcoal by incidental contact with dust and soil. Therefore, it requires precautions
while storing.
Chemical Properties of Charcoal
 Charcoal is a low ash compound. This property of charcoal makes it a high-value
product.
 It is a highly combustible compound.

 It shows high reactivity towards carbon dioxide.

 Charcoal is not easily absorbed in the gastrointestinal (GI) tract
 Charcoal is not metabolized in the body.
  Charcoal is a high surface area compound. Therefore, it absorbs chemicals in the
stomach.

 Charcoal traps the chemicals and carries them out of the body without allowing them
to be absorbed into the blood.
Types of Charcoal
1. Activated Charcoal
2. Wood Charcoal
3. BBQ Charcoal
4. Coconut Shell Charcoal
5. Activated Bamboo Charcoal

5. Explain the following types of charcoal production processes

(i) Earth kiln (ii) Brick kiln (iii) Metal kiln

EARTH KILN:

Earth kilns as the simplest method for charcoal production

Earth pit kilns represent the simplest technology for charcoal production. It is the traditional
way of making charcoal in many parts of the world. The process of using earth pit kilns begins
by stacking wood in a pit, then sealing it with a layer of grass and soil and igniting the wood at
one end, starting carbonization. Earth kilns are usually large and they can use large pieces of
wood, but they can also have small size and be suitable for households. However, the
ventilation system of this type of kilns has some disadvantages. It may be difficult to control
and usually the carbonization is incomplete, producing only low quality charcoal.

Casmance kiln:
The improved earth kilns such as the Casamance kiln and the Swedish earth kiln are
equipped with a chimney. The chimney allows a better control of air flow and reduces heat loss
during carbonization and improves gas circulation, giving a higher quality of charcoal and
efficiency up to 30 %. The charcoal produced in the improved earth kilns has a high proportion
of fixed carbon, low volatile matter and a low bulk density. However, the earth kiln must be
completely rebuilt after each cycle. Its production cycle lasts 24 hours what is too long. The
kiln operation requires considerable skill and experience.
The most common earth kilns are the traditional and improved earth kilns.
BRICK KILN:

The brick kiln is one of the most effective methods of charcoal production, giving the
efficiency of up to 30 %. It is suitable for semi-industrial production of charcoal. However, as
brick kilns are stationary once built, they can only be used in areas with an easy supply of
wood. The kiln could also be built using concrete instead of bricks.

There are many types of brick kilns in the world and most of them give good results. The most
notable designs are the Argentine half orange kiln and the Brazilian beehive kiln. The first
Kiln is made entirely from brick and mud. The carbonisation cycle is much quicker and lasts
13 – 14 days. It is important to know that easy drainage of water away from the kiln is the main
requirement of setting the kiln. The Brazilian beehive kiln is internally heated, fixed, batch
type.

They are circular, have a domed roof and are made of ordinary bricks. The circular wall of the
kiln is in contact with the outside air. The carbonization cycle lasts 9 days with a production of
5t/cycle. It has a high efficiency of up to 62% when properly operated. The life span of the kiln
is up to 6 years on the same site.

STEEL KILN:

Modern methods of charcoal production

Steel kilns are considered as one basis of modern charcoal production. Many different types of
steel kilns have been developed throughout the world. The main difference of steel kilns is in
their capability to carbonize even poor quality wood. What is more, it can easily be transported.
However, still kilns are not suitable for high-volume production as their annual output is only
about 100 – 150 t of charcoal, wherein their efficiency is high (27 – 35 %) and the process of
carbonization is quick (from 16 to 24 hours).

Steel drum kilns facilitate access to sustianably made charcoal as the kilns are low cost, portable
and easy to use. Moreover, the conversion efficiency obtained in oil drum kilns is around 23%.
However, the main disadvantage of the kiln is that the raw material must be less than 30 cm
long and the diameter must be 5 cm, what requires a considerable amount of labour in the
preparation of the raw material.
So, there are three main methods of charcoal production which are represented by many types
of kilns used throughout the world. The earliest method of charcoal production based on using
earth pit kilns. It is still a very popular technology, but the earth kiln operation requires
considerable knowledge and experience, as well it must be completely rebuilt after each cycle.
Today the most popular methods include steel and brick kilns as they are easy to use,
could carbonize even poor quality wood, give high quality charcoal. However, the
carbonisation cycle of steel kilns is much quicker than others and lasts 16-24 hours, wherein it
is highly automated.

6. List out applications of Charcoal in various domains

Metallurgical fuel
Charcoal burns at temperatures exceeding 1,100 degrees Celsius (2,010 degrees Fahrenheit).
By comparison the melting point of iron is approximately 1,200 to 1,550 °C (2,190 to 2,820
°F). Due to its porosity, it is sensitive to the flow of air and the heat generated can be moderated
by controlling the air flow to the fire. For this reason charcoal is still widely used by
blacksmiths.
Charcoal has been used for the production of iron since Roman times and steel in modern times
where it also provided the necessary carbon. Charcoal briquettes can burn up to approximately
1,260 °C (2,300 °F) with a forced air blower forge.
In the 19th century charcoal was largely replaced by coke, baked coal, in steel production due
to cost.
Industrial fuel
Historically, charcoal was used in great quantities for smelting iron in bloomeries and later
blast furnaces and finery forges. This use was replaced by coke in the 19th Century as part of
the Industrial Revolution.
Cooking fuel
Prior to the Industrial Revolution, charcoal was occasionally used as a cooking fuel. Modern
"charcoal briquettes", widely used for outdoor cooking, are made with charcoal but may also
include coal as an energy source as well as accelerants, binders and filler.
Syngas production, automotive fuel
Like many other sources of carbon, charcoal can be used for the production of various syngas
compositions; i.e., various CO + H2 + CO2 + N2 mixtures. The syngas is typically used as
fuel, including automotive propulsion, or as a chemical feedstock.
Pyrotechnics
Charcoal is used in the production of black powder, which is used extensively in the production
of fireworks. It is usually ground into a fine powder, with airfloat grade being the finest particle
size available commercially.
Cosmetic use of bamboo charcoal
Charcoal is also incorporated in multiple cosmetic products. Raw bamboo charcoal is obtained
after drying and carbonization in an oven at elevated temperature.The role of charcoal in
cosmetics is based on its highly effective absorbing properties at a microscopic-scale.
Other applications include:
• Reduces acne and improves skin health
• Whitens Teeth
• Removes bad odor and so on
Carbon source
Charcoal may be used as a source of carbon in chemical reactions. One example of this is the
production of carbon disulphidethrough the reaction of sulfurvapors with hot charcoal. In that
case the wood should be charred at high temperature to reduce the residual amounts of
hydrogen and oxygen that lead to side reactions.
Art
Charcoal is used in art for drawing, making rough sketches in painting and is one of the possible
media for making a parsemage. It must usually be preserved by the application of a fixative.
Artists generally utilize charcoal in three forms:
• Vine charcoal is created by burning grape vines.
• Willow charcoal is created by burning sticks.
• Powdered charcoal is often used to "tone" or cover large sections of a drawing surface.
Drawing over the toned areas darkens it further, but the artist can also lighten (or completely
erase) within the toned area to create lighter tones.
• Compressed charcoal charcoal powder mixed with gum binder compressed into round
or square sticks.
Purification and filtration
Activated carbon
Charcoal may be activated to increase its effectiveness as a filter. Activated charcoalreadily
adsorbs a wide range of organic compounds dissolved or suspended in gases and liquids.
The medical use of activated charcoal is mainly the absorption of poisons.[12] Activated
charcoal is available without a prescription, so it is used for a variety of health-related
applications. For example, it is often used to reduce discomfort and embarrassment due to
excessive gas (flatulence) in the digestive tract.
Horticulture
One additional use of charcoal was rediscovered recently in horticulture.
Animal husbandry
Charcoal is mixed with feed, added to litter, or used in the treatment of the manure.Poultry
benefits from using charcoal in this manner.
Medicine
Charcoal was consumed in the past as dietary supplement for gastric problems in the form of
charcoal biscuits. Now it can be consumed in tablet, capsule or powder form, for digestive
effects.
Other applications include
• Eye inflammation
• Fever
• Wounds
• Blood cleansing agent
• Kidney disorders
• Liver Disease
• Cancer cure
• Constipation

7. a) Define pyrolytic oil?

Pyrolysis oil, sometimes also known as biocrude or bio-oil, is a synthetic fuel under
investigation as substitute for petroleum. It is obtained by heating dried biomass without
oxygen in a reactor at a temperature of about 500 °C with subsequent cooling.
Pyrolytic oil (or bio-oil) is a kind of tar and normally contains levels of oxygen too high to be
considered a hydrocarbon. This high oxygen content result in non-volatility, corrosiveness,
immiscibity with fossil fuels, thermal instability, and a tendency to polymerize when exposed
to air.
Bio-oil fuels generate more than 50% lower NOx emissions than diesel oil in a gas turbine.

b. Explain the manufacturing process of pyrolytic oils briefly

Pyrolysis involves the rapid thermal decomposition of organic compounds by heat in the
absence of oxygen, which results in the production of charcoal, bio-oil, and gaseous products.
Pyrolysis is usually the first chemical reaction that occurs in the burning of many solid organic
fuels such as cloth, like wood, and paper, and also of some kinds of plastic.
Plastic waste is treated in a cylindrical reactor at temperature of 300ºC – 350ºC. Now a day’s
plastics waste is very harmful to our nature also for human beings. Plastic is not easily
decomposable its affect in fertilization, atmosphere, mainly effect on ozone layer so it is
necessary to recycle these waste plastic into useful things. So we recycle this waste plastic into
a useful fuel.

Pyrolysis of waste plastic is a prospective way of conversion of waste plastic into low-emissive
hydrocarbon fuel. Waste plastic materials viz., polyethylene, polypropylene, polystyrene and
polyethylene terephthalate were collected from local convenience store packing materials.
Waste plastic material pyrolysis was conducted as individual plastics and as mixed feed in a
new laboratory scale batch reactor. Hydrocarbon molecules from the basic materials are split
under the impact of catalyst inside the reactor in 70–240 °C. The reduction of process takes
place from 500–600 °C to 240 °C in the presence of catalyst. The analyses of pyrolysis products
suggested that it can be used as a viable alternative to motor fuel.
It was observed that the yield was better in the case of individual plastic material as opposed
to mixed feed in all cases.
The waste to energy technology is investigated to process the potential materials in waste which
are plastic, biomass and rubber tire to be oil. Pyrolysis process becomes an option of waste-to-
energy technology to deliver bio-fuel to replace fossil fuel.
Economic growth and changing consumption and production patterns are resulting into rapid
increase in generation of waste plastics in the world. For more than 50 years the global
production of plastic has continued to rise.
The plastics have become one of the most important and indispensable materials in our
contemporary world. These plastics are not presently biodegradable and are extremely
troublesome components for land filling. The waste plastics are known for creating a very
serious environmental challenge because of their huge quantities and the disposal problems
caused by them. The pyrolysis has a wide temperature range and it can be performed with or
without a catalyst. Generally used catalysts for this process are mordenite, FCC, USY, ZSM-
5, etc.
*In pyrolysis (plastic to oil) process, the plastic waste is not burned. But instead plastic is
chemically broken down into Pyrolysis Oil, Hydrocarbon Gas and Carbon Black.

8. Discuss various applications and yields of pyrolytic oils – in detail

1. Heat and Power

Pyrolysis oil can replace heavy and light fuel oils or natural gas in existing electricity plants.

2. Sustainable transport fuels

Pyrolysis oil as such is not suited for direct use as a transportation fuel. After some further
treatment however it can be co-refined or upgraded to a 2nd generation transport fuel.

3. Bio based Chemicals

Pyrolysis oil contains a large amount of different components and can be the basis for a huge
number of new products and chemicals

4.Diesel Engines

In many areas in the world diesel and natural gas are still being used for diesel engines to
produce power and heat. If in these areas biomass is available the pyrolysis oil can be made
locally and used locally to produce power and heat. Another interesting application is ship
propulsion. In this field the application of pyrolysis oil is one of the few alternatives to fossil
fuels that are commercially attractive. Pyrolysis oil has been tested successfully on stationary
diesel engines. Some changes to the engines are required, mainly to prevent damage to the
engine and fuel system due to water content and acidity of pyrolysis oil. The electrical
efficiency is very high for diesel engines (>40%) compared to all other decentralized
alternatives, including gas turbines and the direct burning of biomass to produce power.
5.Boilers

By direct combustion in a boiler or furnace pyrolysis oil can be used to produce heat. This is
the most simple and straightforward application. In this application pyrolysis oil can replace
natural gas and heavy and light fuel oils, reducing the carbon emissions by around 90%.

With some alterations in the design, pyrolysis oil gives highest efficiency.

9.a) Define Syngas ? How syngas is produced.

Syngas, also called a synthesis gas, is a mix of molecules containing hydrogen, methane,
carbon monoxide, carbon dioxide, water vapours, as well as other hydrocarbons and
condensable compounds. It is a main product of gasification and majority product of high
temperature pyrolysis carried on any biomass, residues and waste. When produced in pyrolysis,
it is created by the vaporisation of volatile compounds from the raw material thanks to the heat,
which induces a set of complex reactions.

The chemical composition of syngas and proportion of its molecules is highly dependent on
the raw material characteristics and conditions of the treatment process. Biogreen technology
allows a consistent generation of syngas fuels thanks to the stable, repeatable treatment
conditions and possibility of adapting the processing temperature according to the demand.

Synthetic Natural Gas production (SNG)

The high-temperature processes of pyrolysis allow to create significant quantities of syngas

with notable concentrations of carbon monoxide, hydrogen and methane. The interest in
production of synthetic natural gas through the methanation of H2 and CO is increasing fast.

(b) Mention primary applications of Syngas in various engineering fields

Hot Syngas has the following applications

• heat production for drying or industrial purposes

• industrial steam or thermal oil production

• replacement of conventional fuel in the existing boilers

• electricity generation via ORC turbine

• electricity generation via steam turbine

Applications focused on using ambient temperature synthetic gas are linked with necessity of
cooling down the syngas and extraction of liquid phase – pyrolysis oil. Electricity generation
through internal combustion engine, or molecules separation, requires high degree of syngas
purity. Process of cooling pyrolysis gas and separating condensable and non-condensable
phases requires additional energy to reduce the managed stream temperatures. As a result,
syngas at ambient temperatures is also easier to transport and offers wider scope of perspectives
for its further treatment, allowing separation of molecules and their further utilisation.

Ambient temperature Syngas applications include

• electricity generation via internal combustion engine

• electricity generation via gas turbine

• methane to grid production

• hydrogen production

• fuel cells utilisation

• other special applications

10. Write short notes on

(i) Slow pyrolysis method

(ii) Flash pyrolysis method

(iii) Fast Pyrolysis

(i) Slow pyrolysis method:
The pyrolysis of biomass undertaken with a heating rate of less than approximately 10°C/min
has long been used for the production of charcoal from wood, and is classified as a slow
pyrolysis process. Here, the biomass is heated to ∼500°C with reaction vessel residence times
for the resulting vapors being of the order of several hours, something that facilitates secondary
reactions between low molecular weight (volatile) components and gives rise to high charcoal
contents and lower liquid yields.

(ii) Flash Pyrolysis

Flash pyrolysis (sometimes called very fast pyrolysis), characterized by rapid heating rates
(>1000°C/s) and high reaction temperatures (900–1300°C), has been shown to afford high
yields of bio-oil with low resulting water content and conversion efficiencies of up to 70%.
The residence times used are even shorter than those of fast pyrolysis, typically less than 0.5s.
To obtain such high heating and heat transfer rates, the biomass feedstock particle size must be
as small as is practically possible, usually around 105–250μm (60–140 mesh size).
(iii) Fast Pyrolysis

Fast pyrolysis is a process in which biomass is rapidly heated to high temperatures in the
absence of air (specifically oxygen). It occurs in a high-temperature range of 425–650°C at a
faster heating rate of 10–200°C/s, with a short solid resistance time of 0.5–10 s and with fine
particle size (< 1 mm) feedstock. In the fast pyrolytic process, biomass decomposes to generate
vapors, aerosol, and some charcoal like char. After cooling and condensation of vapors and
aerosol, dark brown liquid oil is formed. Fast pyrolysis is recommended when the desired
output is mainly liquid and gaseous products. Fast pyrolytic processes produce 60–75 wt% of
liquid bio-oil, 15–25 wt% of solid char, and 10–20 wt% of noncondensable gases, depending
on the feedstock used.