UNIT II

THERMOCHEMICAL CONVERSION
2.1 DEFINITION AND SCOPE OF COMBUSTION/INCINERATION
DEFINITION:

SCOPE:

The scope of combustion/incineration in WTE includes the following key areas:

1. Waste Volume and Mass Reduction

 Reduces the original volume of municipal solid waste (MSW) by up to 90% and
mass by 70–80%.
 Minimizes the requirement for landfill space, making it a space-efficient waste
management option.

2. Energy Recovery

 Heat produced during incineration is used to:

o Produce steam for industrial use.
o Run turbines to generate electricity.
o Provide district heating in colder climates.
 Efficiency can range from 15% to 30%, and in modern plants with cogeneration, it
can go up to 60%.
3. Types of Wastes Treated

 Suitable for:
o Municipal solid waste (MSW)
o Industrial and commercial waste
o Hazardous and biomedical waste
o Sewage sludge and biomass
 Not ideal for wet or non-combustible waste (like metals, glass).

4. Environmental Considerations

 Reduces greenhouse gas emissions compared to landfilling (especially methane).

 Requires flue gas treatment systems (e.g., scrubbers, filters) to control:
o Particulate matter
o Dioxins/furans
o Acid gases (SO₂, NOx)
 Produces bottom ash and fly ash which need safe disposal or reuse (e.g., in
construction).
2.2 ENVIRONMENTAL AND HEALTH IMPACTS OF INCINERATION

1. Environmental Impacts of Incineration

a. Air Pollution

 Dioxins and Furans: These are highly toxic compounds released when chlorine-
containing materials (like PVC plastics) are incinerated.
 Heavy Metals: Emissions may include mercury, cadmium, arsenic, and lead,
which persist in the environment and bioaccumulate.
 Acid Gases: Emissions like SO₂ (sulfur dioxide), HCl (hydrogen chloride), and
NOx (nitrogen oxides) can contribute to acid rain and smog formation.
 Particulate Matter (PM): Fine particles (PM₂.₅ and PM₁₀) can travel long distances
and degrade air quality.

b. Greenhouse Gas Emissions

 Incineration emits CO₂, especially when burning fossil-derived waste (plastics,

synthetic textiles).
 Methane emissions are less than landfills, but the net carbon footprint depends on
waste composition and energy offset.

c. Ash Generation and Toxicity

 Bottom Ash (80–90%): Contains inert residues but may have heavy metals.
 Fly Ash (10–20%): Extremely toxic, requires hazardous waste treatment before
disposal.
 Risk of leachate contamination if not properly managed.

d. Water Pollution

 Scrubber wastewater and ash leachate can contaminate groundwater if improperly

handled.
 Cooling water discharge can cause thermal pollution.

e. Resource Loss

 Incineration may discourage material recovery and recycling by diverting waste that
could otherwise be reused or composted.

2. Health Impacts of Incineration

a. Respiratory and Cardiovascular Issues

 Emissions of PM, NOx, and SO₂ aggravate asthma, bronchitis, and heart diseases.
 Increased risk in vulnerable populations (children, elderly, those with pre-existing
conditions).
b. Cancer Risk

 Long-term exposure to dioxins and furans is linked to cancers (especially breast and
liver cancer), hormonal disruptions, and developmental disorders.
 WHO classifies dioxins as Group 1 carcinogens.

c. Neurological Effects

 Heavy metals like mercury and lead affect brain development in children and cause
cognitive impairments.

d. Psychological Stress

 Communities near incinerators report stress, anxiety, and reduced quality of life
due to odor, noise, and stigma.
2.3 ADVANTAGES AND DISADVANTAGES OF COMBUSTION
2.4 AIR REQUIREMENT FOR COMBUSTION

Combustion is the exothermic reaction of carbonaceous waste with oxygen (O₂), releasing
heat used for power generation or heating.

The reaction must be complete to avoid pollutants like CO, hydrocarbons, or dioxins.

Theoretical Air Requirement (Stoichiometric Air)

 The stoichiometric air is the minimum air required for complete combustion based
on the elemental composition of the waste (C, H, S, etc.).
 Example combustion reactions:

Excess Air Requirement

 In practice, more air than stoichiometric is supplied to:

o Ensure complete combustion (due to mixing inefficiencies)
o Control temperature and reduce emissions
o Avoid formation of CO or unburnt hydrocarbons

Excess air ratio:

2.5 TYPE OF COMBUSTOR
2.6 ENERGY PRODUCTION FROM WASTES THROUGH
INCINERATION

 Heat: Captured via boiler to produce steam.

 Electricity: Steam drives turbine-generator set.
 CHP (Combined Heat & Power): Supplies both electricity and heat.
2.7 CONCEPT AND ADVANTAGES OF GASIFICATION

Gasification is a thermochemical process that converts carbonaceous materials such as

municipal solid waste (MSW), biomass, agricultural waste, and industrial waste into
syngas (synthetic gas), which mainly contains CO, H₂, CH₄, and CO₂.

 It is carried out at high temperatures (800–1200°C) and with limited oxygen or air
(sub-stoichiometric conditions), unlike combustion.
 The generated syngas can be used for electricity generation, heating, or as a
chemical feedstock for producing fuels like hydrogen, methanol, or synthetic diesel.

Process Steps of Gasification

1. Waste Preparation

 Waste is dried, shredded, and sometimes pelletized.

 Moisture and size reduction enhance thermal efficiency.

2. Drying & Pyrolysis (150–600°C)

 Moisture is removed.
 Organic components decompose into char, tar, and volatile gases.

3. Oxidation / Partial Combustion (800–1000°C)

 A limited amount of oxygen is introduced.

 Partial combustion of char produces heat and CO₂.

4. Reduction / Gasification Zone (800–1200°C)

 Char reacts with CO₂, H₂O (steam), and other gases to produce CO and H₂ (syngas).
 Endothermic reactions dominate.
5. Gas Cleaning and Cooling

 Removal of particulates, tars, H₂S, and other contaminants.

6. Utilization

 Clean syngas is used for power generation (via gas turbines or IC engines), fuel
production, or chemical synthesis.

Main Gasification Reactions

Type Reaction Nature
Partial Oxidation C + ½O₂ → CO Exothermic
Complete Oxidation C + O₂ → CO₂ Exothermic
Boudouard Reaction C + CO₂ → 2CO Endothermic
Steam Gasification C + H₂O → CO + H₂ Endothermic
Water-Gas Shift CO + H₂O ⇌ CO₂ + H₂ Reversible
Methanation C + 2H₂ → CH₄ Exothermic

Advantages of Gasification

1. High Energy Efficiency

o Converts waste into valuable syngas with higher calorific value than
combustion gases.
2. Cleaner Energy
o Lower emissions of NOₓ, SO₂, and dioxins compared to incineration.
3. Fuel Flexibility
o Handles a wide variety of wastes including biomass, MSW, industrial waste,
RDF, etc.
4. Recovery of Valuable Products
o Syngas can be converted into hydrogen, synthetic fuels, or chemicals.
5. Volume Reduction
o Up to 90% volume reduction of waste; reduces landfill dependency.
6. Controlled Emissions
o Easy removal of pollutants from syngas before combustion.

Applications in Waste to Energy

 Electricity generation in decentralized power plants.

 Hydrogen production for fuel cells or transport.
 Methanol/DME production.
 Integrated into biorefineries for circular economy.
2.8 TYPES OF GASIFIER

1. Fixed Bed Gasifier

a) Updraft (Counter-current) Gasifier

 Flow: Air enters from the bottom; waste moves from top → bottom.
 Syngas exits from the top.
 Zones (bottom to top): Combustion → Reduction → Pyrolysis → Drying.

Pros:

 High thermal efficiency.

 Handles high-moisture waste.

Cons:

 High tar content in syngas.

 Not suitable for tar-sensitive engines.
b) Downdraft (Co-current) Gasifier

 Flow: Air and waste both move from top → bottom.

 Syngas exits at the bottom.
 Combustion and reduction zones are close.

Pros:

 Low tar content in syngas.

 Suitable for small-scale power generation.

Cons:

 Limited fuel flexibility.

 Requires dry, uniform feedstock.
2. Fluidized Bed Gasifier

a) Bubbling Fluidized Bed (BFB)

 Bed material (like sand) is fluidized with air/oxygen.

 Waste particles are suspended and mixed uniformly.

b) Circulating Fluidized Bed (CFB)

 Higher velocity allows continuous circulation of bed material and waste particles.

Pros:

 High throughput and heat transfer.

 Suitable for MSW, RDF, biomass.
 Uniform temperature; low tar.

Cons:

 Complex operation.
 Erosion and particle carryover issues.
3. Entrained Flow Gasifier

 Finely ground waste/biomass is injected along with oxygen at high velocity.

 Operates at very high temperatures (1200–1600°C).

Pros:

 Very low tar.

 High carbon conversion.
 Suitable for large-scale hydrogen/syngas production.

Cons:

 Requires fine feed particles and high pre-treatment.

 Expensive materials due to high temp/pressure.
2.9 ENERGY PRODUCTION THROUGH GASIFICATION OF WASTES

Anaerobic
Parameter Gasification Incineration
Digestion
Output Syngas (energy) Heat, ash Biogas (CH₄ + CO₂)
Efficiency Medium–High Low–Medium Low
Emissions Low High Very Low
Feedstock Type Dry, solid waste Any combustible Wet organic waste

Syngas is a combustible gas mixture which can be:

 Burned in gas turbines or internal combustion engines for electricity and heat.
 Used to produce methanol, ammonia, or synthetic fuels.
 Purified to extract hydrogen, especially in sustainable hydrogen technologies.

2.10 COMPARISON BETWEEN INCINERATION AND GASIFICATION

Aspect Gasification Incineration

Oxidant Limited oxygen Excess oxygen
Main Product Syngas (CO + H₂) Heat and flue gases
Efficiency Higher (if syngas used) Moderate
Emissions Low (controlled) Higher (needs scrubbing)
Technology Maturity Emerging Established
Suitability for H₂ High Low
2.11 DEFINITION AND MECHANISM OF PYROLYSIS

Mechanism of Pyrolysis:

The pyrolysis mechanism involves complex chemical reactions, and can be broadly divided
into three main stages:

1. Drying Stage (Below 200°C):

 Moisture content of the feedstock is removed.

 No chemical decomposition occurs.
 Only physical evaporation of water.

2. Devolatilization/Thermal Decomposition (200–600°C):

 Breakdown of large organic molecules (like cellulose, hemicellulose, lignin,

polymers) into volatile gases and vapors.
 This is the main reaction zone.
 Key reactions:
o Cleavage of C–C, C–O, and C–H bonds
o Formation of light gases (e.g., CO, CO₂, H₂, CH₄)
o Evolution of bio-oil vapors and tars
o Formation of char (carbonaceous residue)

3. Secondary Reactions (Above 600°C):

 Cracking of larger hydrocarbons into smaller gaseous molecules.

 Polymerization and condensation of tar vapors into more stable bio-oil or char.
 Further reduction of volatile matter in char.

Type Temp (°C) Heating Rate Residence Time Product Focus

Slow Pyrolysis 300–500 Low Long (min–hrs) Char
Fast Pyrolysis 400–600 High (10–200°C/s) Short (1–2 sec) Bio-oil
Flash Pyrolysis >700 Very High Very short (<1 sec) Syngas
2.12 TYPES OF PYROLYSIS
 Heating
Reactor Type Operation Product Focus Typical Feedstock
Rate
Fixed Bed Low Batch Char Biomass, dry waste
Fluidized Bed High Continuous Bio-oil, syngas Biomass, MSW
Rotary Kiln Medium Continuous Char, syngas Tires, MSW, sludge
Auger Reactor Medium Continuous Bio-oil, gas Plastic, food waste
Lab-scale
Batch Reactor Low Batch Biomass, food waste
products
Microwave Semi-
Very High Syngas, liquid Plastic, e-waste
Reactor continuous
Hazardous/industrial
Plasma Arc Very High Continuous Syngas
waste
2.13 OPERATING CONDITIONS AND END PRODUCT
DISTRIBUTION

Temp Residence Typical Product

Pyrolysis Type Heating Rate Major Products
(°C) Time Yield (%)
Long Char: 30–50%,
300– Low (~5– Biochar, gas,
Slow Pyrolysis (minutes to Oil: 20–40%,
500 10°C/min) some bio-oil
hours) Gas: 10–30%
Oil: 60–75%,
400– High (~100– Short (~1–2 Bio-oil, gas,
Fast Pyrolysis Gas: 10–20%,
600 200°C/s) seconds) char
Char: 10–15%
Gas: 70–90%,
Very high Very short Syngas, small
Flash Pyrolysis >700 Oil: 5–15%,
(>1000°C/s) (<1 sec) oil & char
Char: <10%
Oil: ~40–50%,
Intermediate 400– Medium (10– Bio-oil and char
Medium Char: ~20–30%,
Pyrolysis 600 20 seconds) (balanced)
Gas: ~20%
Syngas (H₂,
Plasma 1200– Extremely high Gas: >90%, Slag:
Few seconds CO), vitrified
Pyrolysis 5000+ (arc heat) ~5%
slag
Gas: 30–50%,
Microwave 400– Rapid internal Oil, syngas, char
Few minutes Oil: 30–50%,
Pyrolysis 800 heating (feed dependent)
Char: 10–20%

2.14 USE OF PYROLYSIS PRODUCTS

Product Immediate Use Long-Term/Advanced Use

Biochar Local soil enhancement Climate-smart agriculture, carbon credits
Bio-oil Fuel for heating Bio-refinery input for chemicals/fuels
Syngas On-site energy generation Hydrogen economy, industrial gas supply
2.15 PROPERTIES OF BIO-OIL AND NEED OF ITS UPGRADATION
Physicochemical Properties:

Property Typical Value / Description

Appearance Dark brown, viscous liquid
Odor Pungent, smoky, acidic
Density ~1.1–1.3 g/cm³ (higher than diesel)
Water content 15–40% (from feedstock moisture and reactions)
pH 2.5–3.5 (acidic due to organic acids)
Heating Value (LHV) 15–20 MJ/kg (lower than diesel ~42 MJ/kg)
Viscosity Highly variable; increases over time
Oxygen content 35–50% (causes instability and low calorific value)
Stability Thermally and chemically unstable
Ash content Low to moderate, depending on feedstock
Solubility Immiscible with fossil fuels; miscible with water
Chemical Composition:

Component Category Examples

Acids Acetic acid, formic acid
Alcohols Methanol, ethanol
Ketones Hydroxyacetone, cyclopentanone
Phenols Guaiacol, cresol
Sugars and Oligomers Levoglucosan, furfural
Aldehydes Formaldehyde, furfural
Water Bound and free water

Why Bio-oil Needs Upgradation

Raw bio-oil cannot be directly used as a drop-in fuel in engines or refined without processing.
Upgradation is essential to enhance its fuel properties and compatibility with existing
infrastructure.

Main Challenges:

Issue Impact
High water content Reduces heating value, leads to phase separation
High oxygen content Lowers energy density, causes instability and corrosion
Acidity (Low pH) Corrosive to storage tanks, pipelines, engine parts
Thermal/Storage instability Viscosity increases over time due to polymerization
Immiscibility with petroleum fuels Limits blending without chemical treatment
2.16 UTILIZATION OF PYROCHAR AND GASES