4/15/2024

Thermal Conversion Routes

• Pyrolysis
• Gasification
• Air/Oxygen Gasification
• Plasma Gasification
Thermal Conversion Routes • Combustion /Incineration
• Electricity generation technologies

1 2

Pyrolysis Pyrolysis
➢ Pyrolysis is defined as irreversible chemical change
brought about by heat in the absence of oxygen.
1. Thermal decomposition occurring in the ➢ During pyrolysis biomass undergoes a sequence of
absence of oxygen changes and normally yields a mixture of gases,
liquids and solid.
2. Is always the first step in combustion and ➢ The solid is called charcoal while the condensable
gasification processes liquid is variously referred to as pyroligneous liquid,
pyroligneous liquor, pyroligneous acid or pyrolysis oil
3. Known as a technology for producing charcoal or bio oil.
for thousands of years ➢ The gas is called pyro gas.
➢ Generally low temperatures and show heating rates
results in high yield of charcoal. This type of pyrolysis
is called carbonization

3 4

Pyrolysis Pyrolysis
❖In a now obsolete process for production of methanol,
acetic acid and acetone, biomass is heated in a retort in 1. Partial gasification or pyrolysis
absence of air and the liquid vapors are condensed.
❖This type of pyrolysis is generally called destructive distillation. (heating in the absence of oxygen/air)
❖In a relatively recent development it is found that yields
of volatiles (gas and liquid) increase with the rate of ✓ Solid
heating. At sufficiently high heating rates all biomass
can theoretically be converted to volatiles/liquids. ✓ Liquid
❖This is known as fast pyrolysis. The Future Technology :
Augmentation to crude based fuels
✓ Gas
❖Although pyrolysis (as a process for charcoal making) Complete gasification with air/oxygen and steam
has been known to man since time immemorial, the
complex pattern of series and parallel reactions ✓ Gas
involved in the process is not yet fully understood.

5 6

1
 4/15/2024

Classical Pyrolysis Processes Pyrolysis: Broader mechanism

➢ Low temperature pyrolysis (400-700 oC)
✓ Solid residue maximum

➢ Medium temperature pyrolysis (700-900 oC)

✓ Liquid fraction for chemicals recovery/liquid fuel

➢ High temperature pyrolysis > 900 oC

✓ Gas yield high

➢ The technology of pyrolysis was perfected for

coal: for Blast furnace usage: Coke

7 8

Pyrolysis: Controlling parameters Classification of pyrolysis processes

Pyrolysis processes classified based on heating rates
and residence time
Process Residence Heating Rate Temp (C) Products
Time
Carbonization Days Very low 400 Charcoal
Conventional 5 – 30 min Low 600 Oil, Gas, Char
Fast 0.5 – 5 sec Very high 650 Bio-oil
Flash-liquid < 1 sec High <650 Bio-oil
Flash-gas < 1 sec High <650 Chemicals, Gas
Ultra < 0.5 sec Very high 1000 Chemicals, Gas
Vacuum 2- 30 sec Medium 400 Bio-oil
Hydropyrolysis < 10 sec High <500 Bio-oil
Methanopyrolysis < 10 sec High >700 Chemicals

9 10

Pyrolysis products Pyrolysis: General flow diagram

Biomass/ PRETREATMENT
MSW UNIT LIQUID FRACTION

WATER IN

FLUE GAS REACTOR CONDENSER

WATER GAS FOR

OUT IC ENGINES/
GAS TURBINES/
CHAR THERMAL
GAS FOR REACTOR APPLICATIONS
AIR

11 12

2
 4/15/2024

Fast Pyrolysis Reactor Configurations

➢ Bubbling fluid bed/fluidized bed
➢ Circulating fluid bed
➢ Augur
➢ Rotating cone

13 14

Bubbling fluid bed pyrolysis unit Heating Options

15 16

Bubbling Fluid Bed Reactor Features Circulating Fluid Bed (CFD)

17 18

3
 4/15/2024

Circulating Fluid Bed (CFD) Rotating Cone Reactor

19 20

Rotating Cone Reactor Augur Reactor

➢ Indirect heating system
➢ Yield can be controlled by heating time/augur
speed

21 22

Augur Pyrolysis Reactor System Char Removal Mechanism

Bio oil

Char discharge

23 24

4
 4/15/2024

Liquid Fraction (Bio Oil) Collection Liquid Fraction/ Bio Oil Properties

25 26

Bio Oil Constituents Bio Oil Properties-challenges

27 28

Upgrading of Bio Oil Pretreatment options for co-processing

Vacuum Gas Oil (VGO)

Hyrdogenation at elevated temperatures

R2O + 2 H2 → H2O + 2 RH

29 30

5
 4/15/2024

Fluid Catalyst Cracking (FCC) UOP Fluid Catalyst Cracking (FCC) unit

31 32

Stand-alone refinery for bio oil Applications of Bio Oil

33 34

A new technology for syn gas production Novelty of the process

SYN GAS FOR ❖Pyrolysis in molten cast iron with induction heating
Biomass PRETREATMENT COMBINED CYCLE
UNIT ELECTRICITY ❖The biomass residues are subjected to flash pyrolysis at
GENERATION
WATER IN WATER OUT
1200+ oC
SYN GAS FOR ❖A wide range of size, shape and moisture content
ELECTRIC INPUT OF CONDENSER DG SET FOR
SUITABLE
CORELESS ELECTRICITY tolerance
FREQUENCY
INDUCTION GENERATION
FURNACE WITH ❖The residual carbon, if any, gasified with water/steam
COOLING ALUMINA CRUCIBLE
WATER LIQUID FRACTION ❖The resultant gas comprises of
(LIQUID FUELS)
. CO, H2, CO2, CH4, C2H2 and other higher hydrocarbons
SYN GAS FOR ❖The product gas can be upgraded for ammonia
UPGRADATION TO
MOLTEN SLAG WATER/ COOLING HYDROGEN / F-T synthesis and subsequently other products
STEAM WATER PROCESS

35 36

6
 4/15/2024

Novelty of the process Additional benefits

❖Green Hydrogen a clean fuel can be obtained by further ❖ MSW poses disposal challenges
processing-employing water-gas shift reaction route:
❖ Depending upon heating value: Singularly or co-
hydrogen economy
❖Hydrogen as a feed stock to chemical process industries:
fired mode
in particular refineries ❖ Biomedical waste disposal
❖Electricity can be generated employing combined cycle ❖ The resultant vitreous material for road making
and DG sets Ash is in molten form
❖Liquid hydrocarbons production employing Fischer –
Tropsch process

37 38

Gas composition Green hydrogen production

CO 35 - 42%
Water gas shift reaction
H2 20 - 37%
CH4 5 - 11% CO + H2O ⇌ CO2 + H2
CO2 2 - 7%
C2H2 1 - 3% Pressure, temperature and catalyst important
Higher HCs 1 - 2% parameters
Heating value 17-21 MJ/Nm3
Proven technology with respect to
(High) temperature, catalyst and CO2 removal

39 40

The Syn Gas gas can be used for ammonia synthesis and
urea, nitric acid & ammonium nitrate production
❖ Ammonia synthsis
N2 + H2 ⇌ NH3
Pressure, temperature and catalyst

❖ Urea synthesis
GASIFICATION
2 NH3 + CO2 ⇌ H2N-COONH4 ⇌ (NH2)2CO + H2O
Pressure, temperature and catalyst

❖ Nitric acid and Ammonium Nitrate

4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g)
2 NO (g) + O2 (g) → 2 NO2 (g)
3 NO2 (g) + H2O (l) → 2 HNO3 (aq) + NO (g)
❖ HNO3 + NH3 → NH4NO3

41 42

7
 4/15/2024

Gasification Biomass Thermochemical Conversion

F-T (Fischer-Tropsch)

43 44

Gasification: End products Gasification

Cooling
Condenser
water

Cooling tower

45 46

Gasification Gasification: reactions

Gasification with Oxygen Gas
C + 1/2 O2 CO Composition (oxygen)
(Vol %)
Combustion with Oxygen
C source C + O2 CO2
H2 25 - 30
CO 30 - 60
Gasification with Carbon Dioxide CO2 5 - 15
C + CO2 2CO H2O 2 - 30
CH4 0-5
Gasification with Steam
Oxygen C + H2O CO + H2 H2S
COS
0.2 - 1
0 - 0.1
Gasification with Hydrogen N2 0.5 - 4
C + 2H2 CH4 Ar 0.2 - 1
NH3+HCN 0.0 - 0.3
Water-Gas Shift
Ash/Slag
Steam CO + H2O H2 + CO2
COS: Carbonyl Sulfide
Heating value: 15-20 MJ/Nm3
Methanation With air gasification: 4-5 MJ/Nm3
CO + 3H2 CH4 + H2O
2 CH4 + 2 NH3 + 3 O2 → 2 HCN + 6 H2O

47 48

8
 4/15/2024

Gasification: Gas Composition Gasification: main reactions

Air
Thermochemical Reactions
Steam Temperature specific

Producer Gas
(mol%) with air C + CO2 2 CO (Boudouard)
CO 24 800° - 850° C
H2 13 Fuel Gases
CH4 3 CO + H2O CO2 + H2 (Water gas shift)
CO2 8
N2 52
+
(tars &
particulate)

Heating value : 4-5 MJ/Nm3

49 50

Types of the gasifiers Types of the gasifiers

Design Basis: Fuel Properties, End Use, Scale, Cost Moving/Fixed Bed

1. Moving/Fixed Bed
• Updraft
• Downdraft
2. Fluidized Bed
• Bubbling
• Circulating
3. Entrained Bed/Flow

51 52

Updraft type gasifier Downdraft type gasifier

• Simple, reliable • Requires low moisture
• Commercial history Biomass
(<20%)
• High tars
• Lowest tar
• Thermal applications
• Particle size
Gas, Tar, Water • Gas usage in engines
Pyrolysis (after conditioning)
Reduction
Combustion
Air
• Particle size
Biomass

Air

Pyrolysis
Gas, Tar, Water
Combustion

Reduction

Ash
Roorkee city: Vehicles were running on down draft
gasifiers generated gas in 1940s, Charcoal

53 54

9
 4/15/2024

Fluidized bed gasifier Circulating fluidized bed gasifier

• Highest • Heat carrier is
throughput added-sand
• Fuel flexible • Fuel flexible
• Tolerates moisture • Tolerates moisture
• Complex operation • Very complex
operation
Product Gas

Freeboard

Ash
Fluid Bed
Biomass

Plenum Air/Steam

55 56

Entrained bed gasifier Temperature profiles in gasifiers

Moving Bed Entrained Bed

• Very fine particles

• Fuel flexible
• Dry or slurry
• High energy
Consumption
• High temperatures
• Ash in
liquid/molten form
• Very clean gas :

Fluidized Bed

57 58

Types of gasifiers with advantages and disadvantages Leaders in gasification technology

• Oxygen Blown • Air Blown
− Fluidized Bed
−Entrained Flow
• HT Winkler
• Texaco
• IGT “Ugas”
• E-GAS
• KRW
• Shell
• Foster Wheeler
• Eastman
− Spouting Bed
• Noell
• British Coal
−Fluidized Bed • Foster Wheeler
• HT Winkler − Entrained Flow
• Foster Wheeler • Mitsubishi
−Moving Bed − Transport Reactor
• British Gas • Kellogg
• Sasol − Hybrid (Moving bed)
• Lurgi • Foster Wheeler
−Transport Reactor • British Coal
• Kellogg • ENERCON
• FERCO/Silva

59 60

10
 4/15/2024

Leaders in gasification technology GE Energy Gasifier

61 62

KBR Recirculating Fluidized Bed Gasifier Gasification: High Temperature Winkler (HTW)
Kellogg, Brown & Root (KBR)

Particulate control
device (PCD)

63 64

Gasification: GreatPoint Energy's Bluegas Typical gas heating values

65 66

11
 4/15/2024

Typical gas composition

Gas conditioning

Olivine: magnesium iron silicate

with a melting point of 1900 oC

67 68

Gas conditioning Gas cleaning levels

Impurity Removal level

– Tars H2S, NH3, HCN < 1 ppmv
– Particulates (< 2 micron in size)
HCl < 10 ppbv
– Acid gases ( H2S, NH3, HCN, HCl)
Soot, dust, ash Essentially completely

Tars < 1 ppmv

69 70

Gas conditioning stages Tar reforming

71 72

12
 4/15/2024

Tar reforming: high temperature after filtering High temperature filter: ceramic/metallic candles

catalyst

73 74

Tar reforming prior to filtering Different types of particulate separators

75 76

Purification levels for gas World Syn Gas Market

77 78

13
 4/15/2024

ELECTRICITY GENERATION FROM FUEL GAS ELECTRICITY GENERATION USING GAS TURBINE

1. Gas turbine cycle PREHEATED AIR

HEAT
2. Steam turbine cycle EXCHANGER
VENT
FUEL
3. Combined cycle (Both above combined) GAS/LIQUID
4. Cogeneration: Heat + Electricity

EXAHAUST
5. Integrated gasification combined cycle (IGCC)

TURBINE
COMPRESSED
AIR

COMBUSTION GAS
COMPRESSOR ALTERNATOR
CHAMBER TURBINE

Gas turbines: GE, Siemens, BHEL AIR

ELECTRICITY TO
GRID

79 80

GAS TURBINE WORKING MECHANISM ELECTRICITY GENERATION USING STEAM TURBINE

BHEL, Triveni and others

Supercritical boilers Material of construction, CNG

Material of construction of blades P=218 atm T=374 oC

Babcock and Wilcox: 1867 WATER TO COOLING TOWER

Benson: 1922
CONDENSER
SCB:1957

EXAHAUST
FUEL WATER (COOLING)

TURBINE
GAS/LIQUID/SOLID

STEAM
BOILER ALTERNATOR
TURBINE

AIR
ELECTRICITY TO
GRID
FLUE GASES

81 82

STEAM TURBINE WORKING MECHANISM ELECTRICITY GENERATION THROUGH COMBINED CYCLE

WATER HOT WATER COLD

EXAHAUST
STEAM STEAM
CONDENSER ALTERNATOR
TURBINE

BOILER FLUE GASES

FUEL ELECTRICITY TO
EXAHAUST
TURBINE

GAS/LIQUID GRID

COMBUSTION GAS
COMPRESSOR ALTERNATOR
CHAMBER TURBINE

COMPRESSED AIR AIR

83 84

14
 4/15/2024

Pragati Combined Cycle Power Plant COGENERATION OF ELECTRICTY

1. TARIFF - Rs/kWh
Pragati Power Station, Bawana Industrial Area, Delhi, has an installed capacity 2. BANKING
of 1500 MW BOILER 3. WHEELING

Date of
Stage Unit number Installed capacity Turbine One Nation, one Grid and One frequency
commissioning

STEAM
1st 1 250 2010 Gas turbine-1 One Sun, One World, One Grid
1st 2 250 2011 Gas Turbine-2
FUEL COGENERATION
1st 3 250 2011 Steam Turbine-1 GAS/LIQUID/SOLID ELECTRICITY
1st 4 250 2012 Gas Turbine-3 STEAM
ALTERNATOR TO GRID
TURBINE
1st 5 250 2014 Gas Tubine-4

CONDENSATE

ELECTRICITY
1st 6 250 2014 Steam Turbine-2

STEAM
The largest gas plant in Northern India, and second largest in the country
PROCESS
PLANT

85 86

IGCC CONCEPT-Combined cycle

Solid Fuel

87 88

IGCC CONCEPT-Combined cycle IGCC Plant

89 90

15
 4/15/2024

F-T process
Coal/biomass is hydrogen starved/hydrogen needs to be added to
make it liquid (directly or indirectly)/Hydrogenation of vegetable
oils

1. Bergius process - Pressure/temperature/catalyst

✓ Friedrich Karl Rudolf Bergius (Germany) in 1913
FISCHER-TROPSCH (F-T) PROCESS ✓ Nobel Prize in 1931 (Shared with Carl Bosch)
✓ By end of World War II – most of the liquid fuel for
German army was produced by this method.

2. Fischer-Tropsch process - Mild pressure

✓ Franz Fischer and Hans Tropsch in 1926, Germany

91 92

Ammonia synthesis Bergius process

Haber Bosch process for Ammonia Coal/charcoal T=400-500 oC Hydrogen
Early discovery of Fritz Haber, 1909
P= 20 -70 MPa
Catalyst=Tin
Conver.=97% Fractionating
column
The method was procured by the BASF company and Carl Bosch of BASF converted the process
into the industrial level using a promoted iron catalyst discovered by Allwyn Mittash. Both Haber
and Bosch received Nobel prize for their path breaking discovery in 1918 and 1931 respectively. Pulverizer
Current Industrial Process Bergius HCs
N2 + 3H2
150-250 bar
2NH3 Reactor
300-550 °C
4 beds of Magnetite catalyst
Coal/charcoal
Each pass 15% conversion pasting unit
Overall 97% conversion
Catalyst and promoter are used. The catalyst is partially reduced magnetite (Fe3O4) encased
in a shell of FeO covered by an iron shell. Promoters such as K2O, CaO, SiO2 and Al2O3 are
also used. First Ammonia reactor of
BASF Heavy fraction

93 94

F-T process F-T process

95 96

16
 4/15/2024

FISCHER-TROPSCH (F-T) PROCESS F-T process

T = 200 - 350 oC
Coal/Biomass/NG P = 1 - 25 MPA
CATALYST = IRON OR COBALT BASED

GASIFICATION
UNIT
F-T FRACTIONATING
SYN GAS REACTOR COLUMN
SYN GAS HCS/Alcohols
CLEANING

Methyl tert-butyl ether

(Large number of patents worldwide) (CH3)3COCH3

97 98

F-T process F-T process

99 100

F-T process F-T process

101 102

17
 4/15/2024

F-T process Comparison of catalysts: F-T process

103 104

F-T process F-T process: Technology players

Technology players in this area
1. GE
2. Exxon
3. Shell
4. BP
5. Chevron
6. Sasol
• Afrikaans: Suid Afrikaanse Steenkool en Olie
• English: South African Coal and Oil

105 106

Plasma Gasification
▪ Plasma gasification is an extreme thermal process using
plasma which converts organic matter into syngas.

▪ A plasma torch powered by an electric arc, is used to ionize

gas and catalyze organic matter into syngas with slag
remaining as a byproduct.

Plasma Gasification ▪ It is being used as a form of waste treatment and has been
tested for the gasification of municipal solid waste,
biomass, industrial waste, hazardous waste, and solid
hydrocarbons, such as coal, oil sands, pet coke and oil
shale.

107 108

18

Advantages of Plasma Gasification
• Clean destruction of hazardous waste.
• Preventing hazardous waste from reaching landfills.
• Some processes are designed to recover fly ash, bottom ash, and
most other particulates, for 95% or better diversion from landfills,
and no harmful emissions of toxic waste.
• Potential production of vitrified slag which could be used as
construction material.
• Processing of organic waste into syngas for electric power,
thermal energy and chemicals.
• Production of value-added products (metals) from slag.
• Safe means to destroy both biomedical and many hazardous
wastes.
• Gasification with starved combustion and rapid quenching of
syngas from elevated temperatures can avoid the production of
dioxins and furans that are common to incinerators.
• Air emissions can be cleaner than landfills and some incinerators.
109
Disadvantages of Plasma Gasification
• Large initial investment costs relative to that of
alternatives, including landfill and incineration.
• Operational costs are high due to electric energy
usage.
• Very little or even negative net energy production.
• Wet feed stock results in less syngas production
and higher energy consumption.
• Frequent maintenance.
111
What is plasma?
Sun and Lightning are examples from nature
113
4/15/2024
Dioxins and Furans
Dioxins and dioxin-like compounds (DLCs) are a group of
chemical compounds that are persistent organic pollutants
(POPs) in the environment. They are mostly by-products of
burning or various industrial processes - or, in case of
dioxin-like PCBs and PBBs, unwanted minor components of
intentionally produced mixtures.
Some of them are highly toxic, but toxicity among them
varies 30,000-fold. Toxicity is 100 times of HCN
1. Polychlorinated dibenzo-p-dioxins (PCDDs), or simply dioxins.
2. Polychlorinated dibenzofurans (PCDFs), or furans.
3. Polychlorinated biphenyls (PCBs)
4. Polybrominated analogs
Polybrominated biphenyl (PBB) is as fire retardant in plastic
110
Origin of Plasma
• Plasma is considered to be the fourth state of matter,
consisting of a mixture of electrons, ions and neutral
particles, though it is electrically neutral.
• Discovered by British Physicist Sir William Crookes in 1879.
• The degree of ionization of a plasma is the proportion of
atoms that have lost (or gained) electrons and is controlled
mostly by temperature.
• Heating a gas at very high temperature leads to ionization of
atoms and turns into plasma.
• Natural Plasma can be seen into lightning, sun, stars, comet,
etc.
• Since 1960 it is used by NASA for different operations.
112
Plasma
114
19
 4/15/2024

Plasma Plasma Gasification

Lightning is an example of plasma occurring at Earth's surface.
Typically, lightning discharges 30,000 amperes at up to 100 million
volts, and emits light, radio waves, X-rays and even gamma
rays. Plasma temperatures in lightning can approach 28,000 °C
and electron densities may exceed 1024 m−3.
• Plasma technology involves the creation of a sustained
electrical arc by the passage of electric current through a gas
in a process referred to as electrical breakdown.
• Because of the electrical resistivity across the system,
significant heat is generated, which strips away electrons
from the gas molecules resulting in an ionized gas stream, or
plasma.
• At 2000 °C gas molecules dissociate into the atomic state
and when the temperature is raised to 3000 °C, gas
molecules lose electrons and become ionized.
• In this state, gas has a liquid-like viscosity at atmospheric
pressure and the free electric charges confer relatively high
electrical conductivities that can approach those of metals.

115 116

Plasma: Heat Transfer Mechanism Thermal Plasma Characteristics

• The net energy contributing to heating and melting the particle (Qn) is the
difference between the convective energy transferred from the plasma to the
particle, and the radiative energy loss from the surface of the particle to the
surroundings and is given by
(
Qn = ha(T − Ts ) − a Ts4 − Ta4 ) • An upper temperature limit of 2000 °C can be achieved by burning fossil
• Thermal plasmas have numerous advantages including: high
temperature; high intensity, non-ionizing radiation and high-energy
density.
• The heat source is also directional with sharp interfaces and steep
thermal gradients that can be controlled independently.
fuels, electrically generated thermal plasmas can reach temperatures of
20,000 °C or more.
• Thermal plasma reactors offer a range of other advantages including:
– High throughput with compact reactor geometry;
– High heating rates (>106 K/s) allowing specific gas and solid material
compositions to be obtained;
– Low gas flow rates compared to the combustion of fossil fuels,
thereby reducing the requirements for off-gas treatment.

117 118

Plasma Gasification Plasma Gasification: Features

• Has been proved technically (pilot scale) but not at a
full fledged commercial scale.
• Use of electricity passed through graphite or carbon
Electricity
electrodes, with steam and/or oxygen/air injection
to produce electrically conducting gas (plasma).
Plasma
Plasma
• Temperatures are above 3000 oC.
Torch
System (5000 oC) • Organic materials are converted to syngas
Air/water/
composed of H2 and CO.
Other gases
• Inorganic materials are converted to solid slag.
Plasma Gasification converts solid fuel or • Syngas can be utilized for a variety of uses as
organic waste into a cleaner gaseous fuel explained earlier.

119

119 120

20

Thermal Plasma Types
A. Thermal or equilibrium plasma
– Characterized by a high-energy density and the equality of
temperature of the heavy particles (atoms, molecules and ions) and
electrons.
• Because of their much higher mobility, the energy given to the plasma is
captured by the electrons and transferred to the heavy particles by elastic
collision.
• Due to the high electron number density, associated with operation at
atmospheric pressure, elastic collision frequencies are very high and
thermal equilibrium is reached rapidly.
– Thermal plasma is produced by direct current (DC) plasma torches or
radio frequency (RF) inductively coupled discharges.
121
Plasma Generation: DC based
• An arc is established between an axial, pointed/tip-type
cathode and a toroidal/annular anode.
• The anode is concentric and parallel to the jet axis; the
gas crosses the boundary layer between the arc column
and the anode inner surface, and is pushed downstream
by the pressure of the gas flow.
• The arc attachment point of the anode continuously
changes due to the abatement of the anode electrode
material, whereas the profile of the cathode generally
leads to a fixed plasma arc attachment point.
• To ensure satisfactory working life the electrodes are large
components, making them tolerant of the gradual
abatement and are generally water cooled.
123
Plasma arc torch
In a plasma arc torch, the plasma gas/water/steam serves as
a resistive heating element to convert electricity into heat.
Temperatures in excess of 7000°C can be produced.
Similar to gas welding torch
125
4/15/2024
Thermal Plasma Types
B. Non-equilibrium plasma (or cold plasma)
– Non-equilibrium plasma have lower degree of ionization and are
characterized by lower energy densities and a large difference between the
temperatures of the electrons and the heavier particles.
– Electrons of sufficient energy collide with the background gas resulting in low
levels of dissociation, excitation and ionization without an appreciable
increase in the enthalpy of the gas.
– As a result, the electron temperature exceeds the temperature of the heavy
particles by orders of magnitude and it is possible to maintain a discharge at
much lower temperatures, even at room temperature.
– These plasmas are used for applications such as local surface modification
or surface activation, because the ions, atoms and molecules remain
relatively cold and do not cause thermal damage to the surfaces with which
they come into contact.
– They are used for plasma etching, deposition and surface modification and
for the treatment of heat-sensitive materials, including polymers and
biological tissues.
– These plasmas are produced in various types of glow discharge, low-
pressure RF discharges and corona discharges.
122
Plasma Generation: DC Generation
124
Plasma arc
The water plasma torch in operation with nozzle diameter of
(a) 1 mm, (b) 2 mm, (c) 3 mm
126
21

Plasma Generation: DC
• Wall stabilized or constricted arcs with hot electrodes:
– Torches with a thoriated tungsten cathode and an annular copper anode are typically
used at power levels below 100 kW.
– The most commonly used gases are Ar, He, N2, H2 and mixtures thereof.
– Oxidizing gases cannot be used with this type of torch, since they would oxidize the
tungsten cathode.
– The gas flow rate is generally below 100 L/min and the energy densities in the hot gas
may reach 145 MJ/m3 and the plasma temperatures are between 6000 and 15,000 K.
• Wall stabilized or constricted arc with cold electrodes:
– Torches with cold, copper electrodes (both cathode and anode) of very high thermal
conductivity (385 Wm−1 K−1) can be used for plasmas containing oxidizing gases.
– They have two coaxial, tubular electrodes separated by a small gap in which the
plasma is generated with a strong vortex motion.
– This is induced by either a magnetic field, or a swirl in the gas flow. Industrial versions
of this type of torch have been operated at power levels ranging from 100 kW to 6 MW
with gas flow rates as high as 300 m3/h (5000 L/min) in a 1 MW torch.
127
Characteristics of Plasma Arc Technology
• Plasma acts as a resistive heating element that cannot
melt and fail
• Produces temperatures of 4,000°C to over 7,000°C
• Torch power levels from 100kW to 200 MW produce
high energy densities (up to 100 MW/m3)
• Torch operates with most gases – not a combustion
process
• Elimination of requirement for combustion air
– Reduces gas volume requiring treatment
– Reduces potential for formation of complex organics (i.e.,
dioxins and furans)
129
Thermal plasma treatment of wastes
• The high-energy density and temperatures associated with thermal
plasmas, and therefore fast reaction times, offer the potential for a large
throughput with a small reactor footprint.
• The steep thermal gradients in the reactor permit species exiting it to be
quenched at very high rates, therefore it allow the attainment of meta-
stable states and non-equilibrium compositions, thereby minimizing the
reformation of persistent organic pollutants (POPs).
• The high heat flux densities at the reactor boundaries lead to fast
attainment of steady state conditions, which allows rapid start-up and
shutdown times, compared with other thermal treatments such as
incineration.
• Oxidants are not required to produce the process heat source, as no fuel
is combusted, therefore, the gas stream volume produced is much
smaller than with conventional combustion processes and so is easier
and less expensive to manage.
131
4/15/2024
Plasma Generation: DC
• Cathodes are constructed from either a water-cooled metal or more
usually a refractory material that is consumed slowly by sublimation, e.g.
graphite, tungsten or molybdenum.
– The gas flow rate requirement is less than 200 L/min and energy densities may reach
2800 MJ/m3.
• Anodes are made from metals with high thermal conductivities, such as
copper or silver, and are usually in the form of flat ended cylinders to
distribute the arc attachment.
– The key aspect is to provide sufficient water cooling on the back face of the anode to
prevent melting, which limits the maximum energy densities to about 750 MJ/m3.
• Practically, anodes can only be used with inert monatomic gases
whereas cathodes can be used with diatomic–monatomic gas mixtures.
128
Plasma Torch: RF Inductively Coupled Discharges
• RF discharges are characterized by the absence of
electrodes, which avoids the contamination of the
plasma by metallic vapors, and therefore can be used in
reducing and oxidizing, and other corrosive
atmospheres.
• Energy coupling to the plasma is accomplished through
the electromagnetic field produced by the electrical
induction coil.
• The local power density is lower than that of a DC
plasma.
• The main industrial applications are in the field of
spectro-chemical analysis, synthesis of high-purity
silicon or titanium dioxide pigments, ultra-fine and ultra-
pure powder synthesis; and materials processing and for
the destruction of hazardous wastes.
• They are commonly available at power levels of 100 kW
which severely limits their application.
130
Plasma Temperature Profiles
132
22
 4/15/2024

Plasma gasification: Gas composition MSW vitrification

133 134

Plasma Pyrolysis: Emissions Plasma Gasification: Heavy metal emissions

Permissible Measured
Metal concentration (mg/l) Concentration (mg/l)
Arsenic 5.0 <0.1
Barium 100.0 <0.5
Cadmium 1.0 <0.02
Chromium 5.0 <0.2
Lead 5.0 <0.2
Mercury 0.2 <0.01
Selenium 1.0 <0.1
Silver 5.0 <0.5

135 136

Plasma Pyrolysis: Material & Energy Balance Energy balance of plasma gasification
Gas Heating Value Output
Steam Electricity Input
= 4.30
Negligible

Gas Heat Energy

1.05 MBtu

PLASMA Product Gas

MSW 30,300 SCF
1 Ton – 9.39 Mbtu Heating Value =
33% Moisture
GASIFIER 8.16 MBTU

Electricity
0.56 MWHr – 1.90 MBtu

137 138

23
 4/15/2024

Plasma Gasification: Features Plasma Technology: Waste Handled

• Heavy metals • PCB’s

• Radioactive wastes • Asbestos
• Industrial sludges • Chemical wastes
• Municipal solid waste • Medical wastes
• Electric arc furnace dust • Plastics
• Liquid/solid organic • Used tires
wastes

139 140

Plasma Gasification: Uses Plasma Gasification: Biomedical waste

141 142

Plasma Gasification: Waste tyres Plasma Gasification: Hazardous waste

143 144

24
 4/15/2024

Plasma Gasification: plastics Plasma Gasification: Fly ash

145 146

Plasma Gasification: Oil sludge Plasma Gasification: MSW (USA)

147 148

MSW Solid Byproduct Uses Plasma Torches Used for Waste Gasification
Waste Plasma generation equipment
Molten Stream Salable
Bottom ash from municipal incinerator DC transferred arc (Takuma Co. Ltd.)

Processing Fly ash and sludge from wastewater treatment DC non-transferred arc (experimental equipment)

(Product) Product Uses Fly ash from sanitation centre, asbestos DC non-transferred arc (experimental equipment)

Air Cooling Coarse Aggregate (roads, Bottom ash from hospital incinerator, fly ash
from a power plant
DC transferred arc (Technical University of Lodz,
Poland)
(Gravel) concrete, asphalt)
Fibre reinforced plastic composites (FRPC), gill DC non-transferred arc (Institute Energy Research,
net, waste glass Taiwan)
Water Cooling Fine Aggregate (concrete, Dried sludge from hot galvanising process and a RF plasma reactor (Tekna Plasma Systems)
(Sand) asphalt, concrete products) converter flue dust from steelmaking

Zinc oxide from electric arc furnace AC plasma arc furnace

Water Cooling
Recyclable metals Electroplating sludge DC transferred and non-transferred arc
(Metal Nodules)
Charcoal with NaCl (carbonaceous wastes) DC plasma torch + RF plasma torch (experimental
equipment)
Air Blown
(Rock Wool) Insulation, sound proofing Chlorine-containing wastes DC plasma torch with nebulization system

149 150

25
 4/15/2024

The end
Plasma Torches Used for Waste Gasification

151

26