Thermo Chemical Degradation

UNIT-III
THERMOCHEMICAL PROCESSING
To use the biomass effectively, one
needs to process it
The degree of processing required can be

determined depending on type of the end
use in mind. The objective of processing
is to make biomass easy to handle, with
improved heating value or to convert to
more suitable and usable forms like liquid
or gaseous fuels
Processing could be—physical processing
chemical processing
Physical processing – dewatering, drying,

and/or sizing
Chemical processing -- converting into
char, liquids or
gaseous fuels
Chemical Processes
• Thermochemical • Biochemical
– Combustion
– Biogasification
– Thermal Gasification
– Fermentation
– Pyrolysis
Secondary processing into liquid fuels or hydrogen
Combination of the two: methane converted chemically to

methanol
Producer gas converted to methanol bio-chemically
Growth of Algae
Mechanical Process---extraction of oils

Routes for Utilisation of Biomass
Biomass
Improved solid fuels

(Pellet, Char pellet) Liquid Fuels Gaseous Fuels
Thermo-chemical Thermo-chemical
(Pyrolysis Oil) Gasification
(Producer Gas)
Extraction –Trans-esterification Bio-chemical
Seed based crop Biomethanation
(Biodiesel) (Bio gas)
Bio-chemical
(Ethanol)
Thermo chemical conversion technologies
Process Products Equivalence Ratio
Combustion CO2, H20, and heat ø ≥ 1
Gasification CO,H2,CH4,CO2,N2 ø < 1
Pyrolysis char, liquids and gases ø = 1
Where equivalence ratio is the (A/F actual)/(A/F stoichiometric)

CO2
Air Flaming Heat

combustion
Volatiles
Biomass Heat
Char
Air Heat
Surface
combustion
CO2
Charcoal and coal
• Charcoal is formed from biomass upon processing by
man as against coal which is made from fossils upon
processing by nature
• Coal properties therefore depend on the site of
mining, the weathering conditions it has gone
through
• Charcoal properties will largely depend on the
biomass of origin and the processing conditions
Pyrolysis in which charcoal production is maximised is called carbonisation (*
carbonistation is also used for pyrolysis of coal to make coke)
Uses of charcoal:
Domestic fuel, Barbeque, Heating, Feed material for gasifiers, Activated carbon
and metal industry
Useful byproducts are recoverable
Fuelwood is the primary raw material but these days agroand forest residues
are also potential candidates
Fig. 6 Charcoal Plant with Refinery for Recovery of Chemical By-Products
1. Crude methanol
I. Carbonisation
2. Crude acetic acid
II. Pyrolygneous acid recovery
3. Methanol
III. Crude methanol plant
4. Acetic acid
IV. Acetic acid concentration
5. Methylating spirit
6. Tar
7. Waste water disposal
Yield per 1,000 kg of air dry wood
Acetic acid 50 kg
Methanol 16 kg
Acetone and Methyl Acetone 8 kg
Soluble tars 190 kg
Insoluble tars 50 kg
Charcoal properties as a fuel
i. Burns with less smoke and flame

(depending upon the yield—25%-40%)
(volatile content 5%—25%)
ii. Requires little or no preparation before use
iii. High energy content per unit mass
(also dependent on yield---typically 22-30MJ/kg)
iv.Stored easily—is in the form of briquettes (natural or pelletised)
EFFECT OF WOOD MOISTURE CONTENT ON ENERGY USE
Moisture % Energy used Circulating Electricity

MJ/m3 gas m³ kWh
5 35 210 2.5
10 40 270 3.2
15 154 490 4.4
20 293 770 5.2
25 460 1050 7.2
30 648 1400 9.0
There are two route for making charcoal briquettes
1. B-C (densification and carbonisation

2. C-B ( carbonisation and briquetting
B-C –machines are available for different techniques, raw material and
capacity for densification and then followed by carbonisation in kilns
Advantages: intermediate products in terms of uncarbonised pellets are
available, and conventional kilns can be used
Disadvantages: Higher pressures required, therefore higher energy

input, more wear and tear of the parts and tend to disintegrate to more
fines.and also on exposure to water
C-B – carbonisation followed by briquetting.

Advantages: energy input is less, and less wastage as fines are
pelletised, binders are used
Disadvantages: yield of charcoal is less, and difficult to use the

intermediate product.
Binders used
Organic ---starch, molasses etc
Inorganic– bentonite clay
Organic binders burn well and are used for making briquettes for industrial
purposes
Inorganic binders are used when briquettes are to be used for special
applications where heat release rates are to be reduced,
Biomass Combustion
Biomass combustion :
Domestic cooking ---wood stoves

Domestic boilers ---wood fuelled boilers
Industrial boilers for process heat
Industrial Boilers for power generation
Industrial Boilers for CHP applications
Incinerator, stove, combustor, boiler

Biomass Gasification
Thermo-chemical gasification of biomass:
Definition:
Thermo-chemical gasification is conversion of biomass into gaseous fuels
and more commonly is partial-combustion of biomass in an oxygen-
deficient atmosphere
Types of thermo-chemical gasification:
Classification 1:
Four types: Depending upon the gasifying medium used
 Pyrolysis
 Air gasification
 Oxygen gasification
 Hydro-gasification (steam gasification)
Classification 2:
 Atmospheric gasification
 Pressurised gasification
The main reactions are
1. Combustion Reaction:
C + O2 CO2 + 393800 kJ/kg mole
2. Boudouard Reaction:
C + CO2 2CO - 172600 kJ/kg mole
3. Water Gas Reaction:
C + H2O CO + H2 - 131400 kJ/kg mole
C + 2H2O CO2 + 2H2 - 88000 kJ/kg mole
4. Water Shift Reaction:
CO + H2O CO2 + H2 + 41200 kJ/kg mole
5. Methane Reaction:
C + 2H2 CH4 + 75000 kJ/kg mole
EQUIVALENCE RATIO: [weight of oxidant/weight of dry fuel ]
----------------------------------------------
[stoichiometric oxidant /fuel ]
ER ≥ 1 ---- combustion
ER < 1 ---- gasification/ pyrolysis
ER = 0 ---- pyrolysis
SPECIFIC GASIFICATION RATE: Amount of gas generated per unit area

per unit time
Or amount of biomass gasified per unit area per
unit time
Higher for down draft gasifies in order to achieve good cracking of tar
Thermo-chemical Air-Gasification of Biomass:
Thermochemical Air Gasification is effected in Reactors called Gasifiers
Four types of gasifiers: Based upon the direction of gas/air flow

 Down draft gasifiers
 Updraft gasifiers
 Cross draft gasifiers
 Fluidized bed gasifiers
Each type has its specific virtues and is better suited for specific application
and in a specific situation
Downdraft gasifier Updraft gasifier
Cross Draft Gasifier
About producer gas:
Typical volumetric composition of producer gas is:
CO 15-20%
CO2 10-12%
H2 20-24%
CH4 0-4%
N2 48-52%
Producer gas exits the gasifier at 300 to 4000C
Contains measurable quantity of Condensibles (Tar) & Particulates
( ash, soot etc.,)
This gas is required to be cooled and cleaned before it can be used as an
engine fuel. It can however be used as it comes for Thermal Applications.
Producer gas compared with other fuels:
Fuel Gasoline Diesel Biogas Producer Gas
Composition -- -- CH4 60- CO 15-20%

70% H2 20-24%
CO2 30 – CH4 0-4%
40% CO2 10-12%
N2 48-52%
Density (kg/m3) 713-730 800-840 1.090 1.014
Calorific ~10,500 10,500 4,180 900-1200

Value kcal/kg
~7,130 8,000 4,560 900-1100

kcal/m3
Producer Gas is a LCV gas as against biogas which can be termed as MCV and
Natural Gas as HCV

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UNIT-III

The degree of processing required can be

Physical processing – dewatering, drying,

Secondary processing into liquid fuels or hydrogen

Combination of the two: methane converted chemically to

Producer gas converted to methanol bio-chemically

Mechanical Process---extraction of oils

Improved solid fuels

Combustion CO2, H20, and heat ø ≥ 1

Gasification CO,H2,CH4,CO2,N2 ø < 1

Pyrolysis char, liquids and gases ø = 1

Where equivalence ratio is the (A/F actual)/(A/F stoichiometric)

Air Flaming Heat

Acetone and Methyl Acetone 8 kg

Soluble tars 190 kg

i. Burns with less smoke and flame

Moisture % Energy used Circulating Electricity

1. B-C (densification and carbonisation

Disadvantages: Higher pressures required, therefore higher energy

C-B – carbonisation followed by briquetting.

Disadvantages: yield of charcoal is less, and difficult to use the

Organic ---starch, molasses etc

Inorganic– bentonite clay

Domestic cooking ---wood stoves

Incinerator, stove, combustor, boiler

SPECIFIC GASIFICATION RATE: Amount of gas generated per unit area

Thermochemical Air Gasification is effected in Reactors called Gasifiers

Four types of gasifiers: Based upon the direction of gas/air flow

Composition -- -- CH4 60- CO 15-20%

Calorific ~10,500 10,500 4,180 900-1200

~7,130 8,000 4,560 900-1100

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