Unit 5

Torrefaction
• Torrefaction is a thermochemical treatment of biomass
at 200 to 320 °C (392 to 608 °F). It is carried out under
atmospheric pressure and in the absence of oxygen.
• During the torrefaction process, the water contained in
the biomass as well as superfluous volatiles are released,
and the biopolymers (cellulose, hemicellulose and lignin)
partly decompose, giving off various types of volatiles.
• The final product is the remaining solid, dry, blackened
material that is referred to as torrefied biomass or bio-
coal.
 liquefaction
• The liquefaction of biomass is an important technology
to converse the biomass into valuable biofuel.
• The common technologies for liquefaction of biomass
are indirect liquefaction and direct liquefaction.
• The indirect liquefaction refers to the Fischer–Tropsch
(F–T) process using the syngas of biomass as the raw
material to produce the liquid fuel, including methyl
alcohol, ethyl alcohol, and dimethyl ether.
• The direct liquefaction of biomass refers to the
conversion biomass into bio-oil, and the main
technologies are hydrolysis fermentation and
thermodynamic liquefaction.
• There are two approaches to produce ethyl
alcohol. The first pathway is hydrogenation of
CO
• 2CO + 4H2 → C2H5OH
• The second pathway is hydrogenation of CO2
• 2CO2 + 4H2 → C2H5OH,
 Pyrolysis
• Pyrolysis is the heating of an organic material, such as biomass, in
the absence of oxygen. Biomass pyrolysis is usually conducted at or
above 500 °C, providing enough heat to deconstruct the strong bio-
polymers
• Because no oxygen is present combustion does not occur, rather
the biomass thermally decomposes into combustible gases and bio-
char.
• Most of these combustible gases can be condensed into a
combustible liquid, called pyrolysis oil (bio-oil), though there are
some permanent gases (CO2, CO, H2, light hydrocarbons), some of
which can be combusted to provide the heat for the process.
• Thus, pyrolysis of biomass produces three products: one liquid, bio-
oil, one solid, bio-char and one gaseous, syngas.
 Slow pyrolysis typically happens at a very low
heating rate in the range of 5–10°C / min, this
technique produces an estimate of 43% by
volume of oil. Fast pyrolysis in the contrast has a
higher heating rate in the range of 100 –
200°C/s, and very little residence time during
the reaction
Feedstock for pyrolysis
 Plasma Pyrolysis
• Plasma is the fourth state of matter after solid, liquid,
gas. Plasma’s core temperature is 20,000°K. These are
used in this technology for bond dissociation.
• Pyrolysis is the thermal decomposition of organic materials
at an upraised temperature in the absence of oxygen. The
word is derived from the Greek language, “pyro” means
fire and “lysis” means separation
• Plasma pyrolysis is an extreme thermal process for the
disintegration of organic compounds into gasses and
unreachable solid residue. It is done in an oxygen starved
condition. Organic compounds are degraded into syngas.
Advantages of Plasma Pyrolysis
• The main advantage of this technology are:-
• It prevents hazardous waste from reaching landfills.
• It has no harmful emission of toxic gases.
• Firm slag produced by the process can be used in construction.
• Combustible syngas from biomass can be used to generate electric and
thermal energy.
• Slag produces value-added products like concentrated metals.
• Hazardous, medical, plastic and many other types of waste are destroyed
safely.
• Can be installed at any tourist or hilly locations in the country.
• Emission of non-toxic gasses.
• Harmful gases like dioxins and furans are not formed.
• Eco-friendly and safe way for waste treatment.
• Have no harmful effect on the environment, except carbon dioxide
emission.
• Better alternative against incineration.
Disadvantages of Plasma Pyrolysis
• The main disadvantage of this technology are:-
• The large initial investment, as compared to present
alternatives like incineration and landfills.
• High operation cost compared to incinerators.
• Net energy production is very little or very low. Progressive
developments are being run to gain energy recovery.
• Limited plants are available across the country.
• Frequent maintenance is required to ensure proper
functioning.
• Wet feedstock should be avoided, as it produces fewer syngas
and takes more energy.
 Pyrolysis of MSW
• MSW produces heating value of around 20.57 MJ/kg [13], which can be
utilized in power generation, transportation and various petrochemical
industries. Therefore, MSW has a great potential to produce bio-energy.
• Pyrolysis of municipal wastes begins with mechanical preparation and
separation of glass, metals and inert materials prior to processing the
remaining waste in a pyrolysis reactor. The commonly used pyrolysis
reactors are rotary kilns, rotary hearth furnaces, and fluidized bed
furnaces. The process requires an external heat source to maintain the
high temperature required.
• In pyrolysis of MSW, heat transfer is a critical area as the process is
endothermic and sufficient heat transfer surface has to be provided to
meet process heat requirements.
• The main products obtained from pyrolysis of municipal wastes are a high
calorific value gas (synthesis gas or syngas), a biofuel (bio oil or pyrolysis
oil) and a solid residue (char).
 Pyrolysis of Plastic waste
• In waste plastic pyrolysis, the plastic waste material is subjected to
high temperatures in the absence of oxygen and the presence of a
catalyst to help in the gentle cracking of long chains.
• The gases produced are condensed in the condenser to yield low
sulphur content-distilled waste plastic oil .
• The use of catalysts prevents the formation of dioxins and furans
(benzene ring) during the process . Thermal degradation of plastics
decomposes plastics’ three main fractions, namely, gas, crude oil,
and solid residue.
• The crude oil consists of the higher boiling point hydrocarbons from
the non-catalytic pyrolysis process.
• Efficient production of gasoline and diesel from plastic wastes
requires optimization of parameters like catalysts used, pyrolysis
temperature, and plastic-to-catalyst ratios.
 Pyrolysis of Biomass
• Biomass pyrolysis is a process that breaks down biomass
macromolecules into smaller molecules through thermal cracking.
This process occurs in an oxygen-free or oxygen-limited
environment at high temperatures. The result is three main
products: bio-oil, combustible gas, and biochar.
• Here are some key points about biomass pyrolysis:
• Temperature
• The pyrolysis process is usually carried out at temperatures of
500°C or higher. The temperature at which the process is carried
out affects the yields and compositions of the products.
• Products
• The proportion of bio-oil, biochar, and gas produced depends on
several factors, including the biomass type and the pyrolysis
temperature.
 Pyrolysis of E-waste
• Pyrolysis is a thermochemical process that breaks down organic materials in
electronic waste (e-waste) at high temperatures without oxygen. This process can
recover energy and materials from e-waste, and it can also concentrate metals into
a solid residue.
• Here are some things to know about pyrolysis of e-waste:
• Products
• Pyrolysis produces solid, liquid, and gaseous products in varying amounts,
depending on the material being pyrolyzed and the process conditions. The solid
residue is rich in carbon and is called char. The liquid fraction can contain metals
and PAHs, which can pollute soil and water.
• Benefits
• Pyrolysis can convert low-energy-density waste materials into high-energy-density
fuels. It can also recover valuable compounds, such as plastic oil and syngas.
• Challenges
• Pyrolysis can emit toxic compounds, such as PAHs, VOCs, and particulate
matter. Exposure to these harmful compounds can cause health risks to workers
and the public.
 Types of Pyrolysis
There are generally three types of Pyrolysis:
• Slow Pyrolysis
• Fast Pyrolysis
• Flash Pyrolysis
Slow Pyrolysis: It is characterized by lengthy solids and gas
residence times, low temperatures, and slow biomass heating
rates. It is used to modify the solid material and minimize the oil
produced. On the other hand, fast pyrolysis and ultra-fast (flash)
pyrolysis maximize the gases and oil produced.
• Temperature: Med-high (400-500 °C)
• Residence time: Long (5-30 min)
 Types of Pyrolysis
Fast Pyrolysis: It is a rapid thermal decomposition of carbon-
containing materials in the absence of oxygen in moderate to high
heating rates. It is the most common method used in research and in
practical use. The major product is bio-oil. Pyrolysis is an endothermic
process. Char is accumulated in very large quantities and is to be
removed frequently.
• Temperature: Med-high (400-650 °C)
• Residence time: Long (0.5-2 s)
Flash Pyrolysis: It is a very rapid thermal decomposition pyrolysis
process, the heating rate is also very high. The main products are gases
and bio-oil. Flash pyrolysis produces a very less quantity of gas and tar
as compared to slow pyrolysis.
• Temperature: high (700-1000 °C)
• Residence time: Long (less than 0.5 sec)
 Effect of operating parameter
• Temperature: Temperature is one of the important parameters for the
pyrolysis process. Decomposition and devolatilisation of biomass
components undergo in different temperature ranges. At low temperature
below 300 °C, decomposition of hemicellulose and non condensable gases
produces heavy tars. At high temperatures (>550 °C), decomposition of
biomass to its various fragments produces numerous types of compounds.
• Size of the feed particles: Size of the feed particles affects the yield and
properties of the oil. It is observed that small particle size of biomass is
generally preferred during pyrolysis as they heat up uniformly and easily.
Particle size of <200 mm for rotating cone pyrolysis, <2 mm for fluid bed
systems and<6 mm for circulating fluid beds are suggested as optimum
size.
 Effect of operating parameter
• Residence time: Residence time is an important parameter for the
production of liquid fuels. The optimum residence time to achieve
maximum liquid yield in pyrolysis is of few seconds to few minutes.
Generally, low temperature and low residence time are preferred.
In pyrolysis, as time increases, secondary reaction takes place,
which decreases the yield of liquid product. It is observed that for
complete conversion, the residence time may be larger, but to
attain maximum liquid yield, it should be low.
• Heating rate: The rate of heating is an important factor for
decomposition of biomass into products. In fast pyrolysis, a quick
decomposition of biomass to its components requires high heating
rates. Maximum liquid product is also formed at high heating rates
and short residence times in this process. So, the time of contact of
secondary reaction is less by which less amount of undesired
products are formed.
 Product Characterizatoin: Charcoal
production and gas Utilization
• Charcoal is the traditional fuel of a blacksmith's forge
and other applications where an intense heat is
required. Charcoal was also used historically as a
source of black pigment by grinding it up. In this form
charcoal was important to early chemists and was a
constituent of formulas for mixtures such as black
powder. Due to its high surface area charcoal can be
used as a filter, and as a catalyst or as an adsorbent.
• As pyrolysis gas contains the basic components of
syngas (carbon monoxide, carbon dioxide, and
hydrogen), it could be utilized as an energy source
• Waste gas: There are two kinds of waste gases produced in the
production process of DOING waste tyre pyrolysis plant, one is the
tail gas produced in the pyrolysis reactor while the waste tyre is
pyrolyzed. The other is the exhaust gas generated when heating the
pyrolysis reactor. The first type of waste gas is non-condensing but
combustible gas, which will be recycled back to heat the pyrolysis
reactor. The second type of exhaust gas will be cleaned by a flue gas
purification system that includes water dust scrubber, pulse dust
collector and desulfurization & purification tower.
• Waste solids: The residue left in the pyrolysis reactor of DOING
waste tyre pyrolysis plant is also called carbon black. It is a by-
product of the pyrolysis of waste tyre. It can be sold directly,
pressed into briquettes for fuel or ground into powder for making
pigments.
 Environmental effects of pyrolysis
• pyrolysis facilities are energy intensive. They can
also emit carbon monoxide, nitrogen oxides and
sulfur dioxide, leading to air and water pollution.
• Water management is also an essential part of
pyrolysis recycling technologies, with energy use
being just one of the issues. Access to water
sources for cooling products also adds difficulties.
The process uses large amounts of energy and
water, which increases production costs. Also
problematic is the issue of water pollution from
waste streams
 Pyrolysis of Solid Waste for Bio-Oil and Char
Production in Refugees’ Camp: A Case Study
• The MSW samples were taken from Zaatari SyrianRefugee
Camp.
• The MSW pyrolysis was conducted using tubular fluidized
bed reactor (FBR) under inert gas (Nitrogen) at 500◦C with
20◦C/min heating rate and using average particles size 5–10
mm. The products of MSW pyrolysis reaction were:
pyrolytic liquid, solid char, and gaseous mixture
• The elemental analysis results showed that oil product
content consists of 55% C, 37% O2, and the (High Heating
Value)HHV is 20.8 MJ/kg. The elemental analysis of bio char
showed that bio char content consists of 47% C, 49%O2,
and HHV is 11.5 MJ/kg