disposal of toxic and non-toxic waste through lasers641594/fulltext01.pdf · a solar pumped laser...
TRANSCRIPT
Author: Ali Islam
Date: 30-05-2013
Supervisor :Dr. Muhammad Muddassir Silvio Gualini, Dr. Anders
Eliasson, Dr. Hasse Fredriksson
Masters Thesis in Materials Processing
Department of Materials Science and Engineering
KTH-Royal Institute of Technology, Stockholm Sweden
Masters Thesis, KTH- Royal Institute of Technology, Stockholm Sweden
Disposal of Toxic and Non-Toxic Waste through Lasers Destruction of toxic solids, liquids and gases Models and Experimental Results
Abstract
The report discusses the destruction of toxic and non-toxic solids, liquids and gases through
lasers. In order to completely understand the project first chapters describes the basics about
laser and plasma separately, from definition to types, components and categories. Differences
between laser and microwave system are covered in this chapter as well. Besides lasers there are
different technologies that are currently being used to destroy toxic and non-toxic materials.
These technologies were studied and comparison tables are made in order to discern between
different destruction technologies. For the destruction of toxic and non-toxic materials through
lasers two mathematical models have been developed, molecular dissociation model and plasma
exploitation model, and later the experimental work was carried out on one of the toxic material.
Mathematical modeling and experimental work is in accordance with each other as discussed in
results and discussion. Mathematical model shows that all the materials discussed in the report
can be destroyed by lasers but in order to carry further experiments on all other toxic and non-
toxic materials, a proposal is made for the laser reactor using CAD model (Solid Edge) and
drawing software (AutoCAD). Tables and mathematical calculations have been placed in
appendix at the end of the report.
Preface:
This project is a portion of a big idea of Dr. Muhammad Muddassir Silvio Gualini which is to
generate electrical power through solar pumped lasers. The original idea was to use solar
pumped lasers to destroy toxic and non-toxic waste materials. Solid, liquid and gas toxic
materials listed were supplied by AMIAT, the public company in Torino collecting house and
toxic waste. The laser action on the waste materials will produce plasma and a catalyst will
transform the extremely hot and high pressure plasma into a high temperature and high pressure
inert gas (not-toxic, not-smelling). Generation of high temperature gas can be used to generate
electricity through gas turbine. In order to obtain the optimal turbine parameters of gas
temperature and pressure the inert gas is previously cooled through heat exchangers generating
hot water to be supplied to for house hold purposes. The focus of this report is on the destruction
of toxic and non-toxic materials through lasers. The destruction of toxic materials is studied by
two mathematical models. First the molecular dissociation model is used to calculate the
destruction of toxic materials and then the plasma exploitation model is used. There are different
ways of destruction of toxic materials as well which are currently being employed as well but
either their cost is extremely high or they produce by products which are dangerous. A solar
pumped laser or a laser powered by part of the energy generated by the gas turbine (co-
generation) or by a solar panel or thermal unit. In any case one of these three solutions would
eliminate the running cost factor of the laser can be almost eliminated. In any case the proposed
and discussed method grants the 99.5% destruction of toxic and non-toxic materials. The
mathematical models prove the assertion.
Contents
1. Basics about laser and plasma .............................................................................................................. 1
1.1. Laser ............................................................................................................................................. 1
1.1.1. Abbreviation .......................................................................................................................... 1
1.1.2. Definition............................................................................................................................... 1
1.1.3. How to produce laser light? .................................................................................................. 1
1.1.4. Components of lasers ........................................................................................................... 2
1.1.5. Categories of lasers ............................................................................................................... 4
1.2. Plasma ........................................................................................................................................... 4
1.2.1. Common forms of Plasma ..................................................................................................... 5
1.2.2. Degree of Ionization .............................................................................................................. 5
1.2.3. Temperature measurement of plasma ............................................................................... 6
1.2.4 Density of plasma .................................................................................................................. 6
1.2.5. Potential of Plasma ............................................................................................................... 7
1.2.6. Magnetization ...................................................................................................................... 7
1.2.7. Mathematical description of plasma .................................................................................... 7
1.3. Laser confinement of plasma ........................................................................................................ 8
1.3.1. LIBS in brief........................................................................................................................... 8
1.3.2. Life cycle of LIBS process ..................................................................................................... 10
1.3.3. Advantages of LIBS .............................................................................................................. 11
1.4. Differences between laser and microwave systems................................................................... 15
2. Overview of current technologies to treat toxic material .................................................................. 16
2.1. Thermal Energy: Incineration and pyrolysis ................................................................................ 16
2.2. Plasma Energy: ............................................................................................................................ 19
2.3. Microwave Energy: ..................................................................................................................... 21
3. Comparison tables for destruction of selected toxic materials through different technologies ....... 24
4. Molecular dissociation model ............................................................................................................. 27
4.1. Solids ........................................................................................................................................... 27
4.1.1. Zinc Sulfide, ZnS .................................................................................................................. 27
4.2. Gases ........................................................................................................................................... 31
4.2.1. NO ....................................................................................................................................... 31
4.2.2. NO2 ...................................................................................................................................... 32
4.3. Calculations for number of photons to destroy toxic materials ................................................. 32
4.4. Material destroyed rate by CO2 Gas Dynamic Laser ................................................................... 37
4.4.1. Solids ................................................................................................................................... 38
4.4.2. Gases ................................................................................................................................... 39
4.4.3. Liquids ................................................................................................................................. 40
5. Plasma exploitation ............................................................................................................................. 47
5.1. Solids ........................................................................................................................................... 50
5.2. Gases ........................................................................................................................................... 52
5.3. Liquids ......................................................................................................................................... 53
6. Proposal of laser reactor for decomposition of toxic materials ......................................................... 63
7. Experimental decomposition of NOx................................................................................................... 70
8. Results and Discussion ........................................................................................................................ 73
8.1. Experimental Results and Discussion .......................................................................................... 73
8.2. Methematical models results and discussion ............................................................................. 75
8.3. Conclusions from results and discussion .................................................................................... 80
9. Acknowledgments ............................................................................................................................... 81
10. References ...................................................................................................................................... 82
Appendix ................................................................................................................................................... 103
1. Solids ............................................................................................................................................. 103
1.1. Phosphors ............................................................................................................................. 103
1.2. Asbestos ................................................................................................................................ 108
2. Gases ............................................................................................................................................. 114
2.1. NOx ........................................................................................................................................ 114
2.2. CFC ........................................................................................................................................ 123
2.3. HCFC ...................................................................................................................................... 136
3. Liquids ........................................................................................................................................... 143
3.1. Acids ...................................................................................................................................... 143
3.2. Bases ..................................................................................................................................... 161
3.3. Organic Solvents ................................................................................................................... 179
4. Liquids ........................................................................................................................................... 199
4.1 Sulfuric Acid, H2SO4 ............................................................................................................... 199
4.2 Nitric Acid, HNO3 ................................................................................................................... 199
4.3 Acetic Acid, CH3COOH ........................................................................................................... 200
4.4 Hydrochloric Acid, HCl........................................................................................................... 200
4.5 Hydrogen Bromide, HBr ........................................................................................................ 201
4.6 Hydrogen Iodide, HI .............................................................................................................. 201
4.7 Boric Acid, H3BO3 ................................................................................................................... 202
4.8 Oxalic Acid, C2H2O4 ................................................................................................................ 202
4.9 Formic Acid, HCOOH ............................................................................................................. 203
4.10 Citric Acid, C6H8O7 ................................................................................................................. 203
4.11 Benzoic Acid, C7H6O2 ............................................................................................................. 204
4.12 Hydrogen Peroxide, H2O2 ...................................................................................................... 204
4.13 Ammonia, NH3 ....................................................................................................................... 205
4.14 Calcium Hydroxide, Ca(OH)2 ................................................................................................. 205
4.15 Calcium Oxide, CaO ............................................................................................................... 206
4.16 Sodium Bicarbonate, NaHCO3 ............................................................................................... 206
4.17 Sodium bicarbonate, NaHCO3 ............................................................................................... 207
4.18 Sodium Carbonate, Na2CO3 ................................................................................................... 207
4.19 Barium Hydroxide, Ba(OH)2, Born Haber cycle ..................................................................... 208
4.20 Strontium Hydroxide, Sr(OH)2 ............................................................................................... 209
4.21 Aluminum Hydroxide, Al(OH)3 .............................................................................................. 210
4.22 Sodium Hydride, NaH ............................................................................................................ 211
4.23 Sodium Hydride, NaH ............................................................................................................ 211
4.24 Potassium Hydroxide, KOH ................................................................................................... 212
4.25 Lithium Hydroxide, LiOH ....................................................................................................... 212
4.26 Magnesium Hydroxide, Mg (OH) 2......................................................................................... 213
4.27 Sodium Hydroxide, NaOH ..................................................................................................... 214
4.28 Ethanol, C2H5OH .................................................................................................................... 215
4.29 Methanol, CH3OH .................................................................................................................. 215
4.30 Propanol, C3H7OH ................................................................................................................ 216
4.31 Tetrachloroethylene, C2Cl4 .................................................................................................... 216
4.32 Toulene, C7H8 ........................................................................................................................ 217
4.33 Chloroform, CHCl3 ................................................................................................................. 217
4.34 Benzene, C6H6 ........................................................................................................................ 218
4.35 Acetone, C3H6O ..................................................................................................................... 218
4.36 Methyl tert-butyl ether, C5H12O ............................................................................................ 219
4.37 Propylene carbonate, C4H6O3 ................................................................................................ 219
4.38 Methylene Chloride, CH2Cl2 .................................................................................................. 220
4.39 n-heptane, C7H16 ................................................................................................................... 220
4.40 Isopropanol, C3H8O ............................................................................................................... 221
1
1. Basics about laser and plasma
1.1. Laser
1.1.1. Abbreviation
Laser stands for Light amplification by stimulated emission of radiations. The way laser light is
different from the monochromatic, bulb light and sunlight is demonstrated Table 1.1.1.
Table 1.1.1: Comparison of laser light with other sources of light, [1]
Type Color Direction of all the waves
Light bulb Not monochromatic Not same Sunlight Not monochromatic same
Monochromatic Monochromatic Not same Laser Monochromatic same
1.1.2. Definition
To be a laser light has to fulfill following two criteria, [1]
It should be monochromatic. Which means it should have the same color. That means all
the wave lengths are equal. I.e. crests and troughs line up with each other.
All the waves move in the same direction or all the particles are moving in the same
direction
1.1.3. How to produce laser light?
When a photons coming at a high speed hits an atom. Electron jumps to a higher energy level.
When it jumps back to lower energy level, it emits photon of the same color but in random
direction, whereas incoming photon disappears. [1]
When a photon coming at a high speed hits an atom, which is already excited the electrons jumps
to a higher energy level and when it jumps back to the lower energy level. It emits photon of the
same color and in the same direction. This time the incoming photon is not disappeared. This
process is called “stimulated emission”. [1]
2
When one high speed photon hits an excited atom two photons are created. When these two
photons hit two other excited atoms four photons are created. In this way “light amplification”
occurs by stimulated emission. [1]. It is demonstrated in Figure 1.1.1.
Figure 1.1.1: Dual nature of light shown as photons [1]
Light has a dual nature. It behaves as particle as well as waves. When an electromagnetic waves
hits an excited atom. After interaction it takes the energy of the atom. The wavelength remains
the same whereas amplitude increases [1]. Wave nature of light is demonstrated in Figure 1.1.2.
Figure 1.1.2: Dual nature of light shown as wave [1]
Excitation of atoms is called “Population Inversion” and it can be done in two ways, [1]
Pumping electrical energy to the atoms which have to be excited
Shinning different colored light at the atoms which have to be excited
1.1.4. Components of lasers
There are four primary components of lasers [2]
1.1.4.1 Active Medium
Active medium is excited by the external energy source to generate photons
3
There can be four types of active medium
Solid Crystals for example Nd:YAG, Ruby
Liquid dyes
Gases such as CO2 or Helium/Neon
Semiconductors such as GaAs
1.1.4.2 Excitation Mechanism
Excitation mechanism is used to pump energy into the active medium and excite it. It can be
done by three different methods. Electrical, optical or chemical
1.1.4.3 Mirror with high reflection
On one side there is a mirror which has very high reflection. It should ensure 100% reflection.
1.1.4.4. Mirror with partial transmission
On the other side there is a mirror which has ordinary reflection. It transmits some of the light
and reflects some of the light.
Figure 1.1.3. demonstrates that there is electrical source which is used as excitation mechanism
which is used to excite the Chromium atoms in Ruby. The photons oscillate between the two
mirrors and transmitted through one of the mirror in the form of laser beam.
Figure 1.1.3: Excitation of Chromium atoms in Ruby [2]
4
1.1.5. Categories of lasers
Lasers can be classified in two categories, [3]
1.1.5.1. Continuous Lasers
Continuous lasers use gas as active medium. They operate for periods more than a second. Laser
pointer is their example. They have high average power (average power means total energy
produced in one second) in comparison with pulsed lasers.
1.1.5.2. Pulsed Lasers
Pulsed lasers use solid crystal, glass or a semiconductor as active medium. They operate for
periods less than one second. They have very low average power in comparison with continuous
lasers.
Pulsed lasers have two types, [3]
1.1.5.2.1. Short Pulsed Lasers
Short pulsed lasers have the duration of one picosecond.
1.1.5.2.2. Long Pulsed Lasers
Long pulsed lasers have the duration of one nanosecond.
1.2. Plasma
Plasma is known as fourth state of matter. In simple words plasma is defined as an ionized gas. It
can consist of electrons, protons, ions which are called as free charge particles. Due to free
charge particles plasma can carry electric current and generate magnetic field. [8]
5
Atoms of a gas contain equal number amount of negative and positive charge. The number of
protons inside the nucleus is equal to the number of electrons revolving around the nucleus.
When the electrons revolving around the nucleus are ejected out of the atoms by providing them
energy, the gas atom becomes ionized. When the number of ions formed to reach to an extent
that they affect the electrical characteristics of the gas then it is called as plasma. [8]
1.2.1. Common forms of Plasma
There are three forms of plasma [4]
Artificially produced plasma
Terrestrial plasmas
Space and astrophysical plasmas
Table 1.2.1 demonstrates the examples of three different forms of plasma
Table 1.2.1: Different forms of plasma, [4]
Artificially produced plasma Terrestrial plasma Space plasma
Plasma displays, e.g. TV Fire Sun and stars
Fluorescent lamps Lightning Solar wind
Area in front of spacecraft’s
heat shield during entering
into atmosphere
St. Elmo’s fire Space between planets
Plasma torch, Electric Arc Sprites, elves, jets Space between stars
Plasma globe Ionosphere Space between galaxies
Dielectric layers Polar aurorae Interstellar nebulae
1.2.2. Degree of Ionization
For plasma, degree of ionization is directly proportional to the atoms which have lost the
electrons and it depends upon the temperature. The mathematical relation for degree of
ionization is given by following relation where ni = number density of ions and na = number
density of neutral atoms [4]
6
1.2.3. Temperature measurement of plasma
The temperature of plasma is measured either in Kelvin or electron volts and this temperature is
the measurement of the thermal kinetic energy of all the particles. There may be a difference
between the ion temperature and the electron temperature. There is a huge difference between
the mass of electrons and the ions; this helps electrons to reach thermal equilibrium much earlier
than then ions or neutral atoms. On this temperature difference basis plasmas can be divided into
two types. [4]
1.2.3.1. Thermal plasma
The plasmas in which electrons and the ions or the neutral particles have the same temperature
are called as thermal plasmas.
1.2.3.2. Non Thermal Plasma
The plasmas in which ions and the electrons are not at the same temperature are called as non-
thermal plasmas. In this case, the ions or the neutral atoms can have as low temperature as room
temperature.
1.2.3.3. Hot Plasma
The plasma which has high degree of ionization is called as hot plasma.
1.2.3.4. Cold Plasma
The plasma which has low degree of ionization is called as cold plasma.
1.2.4 Density of plasma
Density of plasma is defined as number of free electrons per unit volume [4]
7
1.2.5. Potential of Plasma
The potential which exists between the charged particles i.e. ions is called as the potential of
plasma. When an electrode is inserted in the plasma, the potential on the electrode will be less
than that of the plasma due to the formation of Debye Sheath. Electric fields in the plasma are
very small because of good electrical conductivity. There is a concept called quasineutrality,
according to which the density of negative charges can be approximated equal to the density of
positive charges considering large volume. But the concept of quasineutrality may not hold true
at Debye Length. To produce plasma which does not hold the concept of quasinuterality is also a
possibility. [4]
1.2.6. Magnetization
Only that plasma is called magnetized in which the motion of the charged particles can be
influenced by the magnetic field. It can also happen that electrons get magnetized whereas the
ions remain non-magnetized. The special thing about magnetized plasma is that its properties in
the direction of magnetic field are different than the properties in the perpendicular direction.
The relation between electric and magnetic field is given by [4]
E= Electric field
V= Velocity
B= Magnetic field
1.2.7. Mathematical description of plasma
There are two ways to describe the mathematical model for plasma [4]
1.2.7.1. Fluid Model
8
With the help of fluid model the average velocity around each position and density can be
measured. When the plasma velocity distribution is close to Maxwell-Boltzmann distribution
which means collisionality is very high, fluid models are very accurate.
1.2.7.2. Kinetic Model
With the help of kinetic model the velocity of the particle at each point in a plasma can be
measured which requires no need for Maxwell-Boltzmann distribution.
1.3. Laser confinement of plasma
1.3.1. LIBS in brief
It is one of the methods of atomic emission spectroscopy (AES).High powered lasers are used to
produce plasma. Pulses from a laser are focused on the mirror. Mirror reflects the laser pulse
towards the target. Between the target and the mirror and center lens is placed. Fiber optic cable
is then used to collect the plasma light. Spectrometer is used to collect the signal. Each laser
pulse from the laser gives one reading of LIBS (Laser Induced breakdown spectrometry)
measurement. Seen from a naked eye, plasma appears like a flash of a focal volume of bright
white light. This flash of bright white light is accompanied by a loud sound as well. As the
optical breakdown results in the shock waves which produce the loud sound. When the spherical
lens is used for the formation of plasma, the plasma formed is spherical. It happens because the
gas breaks down first at the focal point and then it is extended towards the spherical lens [5].
Figure 1.3.1 demonstrates the apparatus for LIBS.
9
Figure 1.3.1: LIBS apparatus, L=Laser, M=Mirror, LP=Laser Pulse, CL=Lens, P=Plasma, T=target, FOC=fiber optic cable, S=Spectrograph, AD=Array detector, GE=Gating Electronics, C=Computer, [5]
Figure 1.3.2 and figure 1.3.3 demonstrate the two examples for the formation of plasma with the
help of spherical and cylindrical lens on soil and filter respectively.
Figure 1.3.2: Laser Plasma formed on soil by a spherical lens (4-5 mm in length), [5]
Figure 1.3.3: Laser plasma formed on a filter by a cylindrical lens (7-8 mm in length), [5]
10
1.3.2. Life cycle of LIBS process
There are two steps involved in the laser induced breakdown. In the first step, with the help of
few photons free electrons are generated. These free electrons are the initial receptors of energy.
In the second step, avalanche ionization occurs in the focal region. As the number of free
electrons grow, collisions occur which result in ionization and eventually result in the generation
of more free electrons and eventually avalanche occurs. Breakdown threshold can be defined as,
“Minimum irradiance required for the generation of plasma”. [5]
The generation of plasma occurs in a focal volume. After the breakdown, the plasma from the
focal point tends to expand in all directions. But this expansion is more in the direction of the
lens as the laser energy is coming form that direction. When the plasma expands in all directions,
it can have a pear shaped or cigar shaped appearance. The plasma goes through different
transient phases from its initiation to the decay time. The propagation and expansion of the
plasma can be described by three different wave models. [5]
Laser-Supported Combustion (LSC)
Laser-Supported Detonation (LSD)
Laser-Supported Radiation (LSR)
The models of LSC and LSD describe the experiments in case of low irradiances. Plasma at low
irradiance has low temperature and density. When the plasma is expanding, plasma itself and its
boundary with the atmosphere is allowing transmittance to the laser radiation. During expansion
plasma emits different signals and loses the energy in different ways. Afterwards plasma starts
cooling and decaying. Eventually the electrons and the ions recombine and form neutrals. The
mode of heat transfer is either conduction or radiation. The temperature of plasma can rise to
tens of thousands of degrees. [5]. LIBS life cycle is demonstrated by Figure 1.3.4.
11
Figure 1.3.4: LIBS life cycle, [5]
1.3.3. Advantages of LIBS
Like all AES methods, LIBS has following to advantages over non-AES methods. [5]
Ability to detect all the elements
Simultaneous multi-element detection capability
Comparing with other AES-methods, LIBS has following advantages [5]
Rapid
Real time analysis
Simple
Preparation of sample is not a requirement
12
Allows in situ analysis, requiring only optical access to the sample
Can be used on solid, liquid and gaseous samples
Robust plasma can be formed which is not possible under conventional plasmas
Variety of measurement scenarios
1.3.3.1. Variety of measurement scenarios
There are different methods devised for the direction of laser light on the sample. In some
methods the target is very close to the laser and in other methods the target is meters away from
the laser. [5]
1.3.3.1.1. Direct analysis
In direct analysis the lens used has a short focal length. Laser light passes through this short focal
length laser and falls on the target to form plasma. The target can be either solid, gas or liquid.
Fiber optic cable collects the plasma light and transfers it to the spectrograph. Instead of optic
cable a lens can be used as well.
1.3.3.1.2. Fiber optic delivery
By this method the laser pulse at a distance of 100 m can be transferred. Megawatts per
centimeter square power densities can be transferred from one end of the optical fiber to the
other end. After the generation of plasma, energy in the range of tens of mJ can be transported
back. For the back transportation either the same cable can be used or another optical cable can
be used. Figure 1.3.5 demonstrates fiber optic delivery.
13
Figure 1.3.5: Fiber optic delivery; P=Plasma; T=Target; CL=Lens; FOC= fiber optic cable; I=Pulse Injector for FOC; B= Beam splitter; L=Laser; AD=Array Detector; S=Spectrograph, [5]
1.3.3.1.3. Compact probe
Portability is the benefit achieved by this method. It has laser, focusing optics and fiber optics
which ensure the collection of laser pulse and the transportation of plasma light. Both the laser
and the spectrometer are connected to the probe through the electrical cables and they are placed
away from the probe. Compact probe has an edge over the fiber optic deliver because of the
small spot size which results in the delivery of high power density. Figure 1.3.6 demonstrates
compact probe.
Figure 1.3.6: Compact probe; T=Target; P=Plasma, CL=Lens; LP=Laser Pulse; L=Laser; FOC=Fiber optic cable; EC=Electrical cables; AD=Array detector; S=spectrograph; LPS=Laser power supply, [5]
1.3.3.1.4. Stand-off analysis
In this method there is a distance between the laser and the target. Thus a lens of long focal
length is used. The distance between the laser and the target depends upon the laser power, laser
14
pulse energy, beam divergence, spatial profile and the focal length of the optical system. Figure
1.3.7 demonstrates stand-off analysis.
Figure 1.3.7: Stand-off analysis; T=Target; P=Plasma, LP=Laser pulse; B=Beam-splitter; BE=Beam expander; FOC=fiber optic cable; S=Spectrograph; AD= Array detector, [5]
1.3.3.2. No Sample Preparation
Most of the AES methods require sample preparation between LIBS does not require sample
preparation or very little. It is because it’s the same focal volume where the ablation and
excitation occur. Non-conducting and refractory compounds can be vaporized even because of
the high focused power densities. Though no sample preparation is required yet in case of bad
surface ablation pulses can be used. [5]
1.3.3.3. In Situ Analysis
Sample in case of AES methods is brought close to the sample whereas in LIBS source is
brought to the sample. But the distance between the sample and the instrument can be as short as
a few centimeters but in case of standoff analysis this distance can be in meters. [5]
1.3.3.4. Speed of analysis
In case of LIBS, analysis speed is very short because of following reasons [5]
No sample preparation
15
Simplicity of LIBS
Short life time of plasma
Minimal processing time for the spectrum
1.4. Differences between laser and microwave systems
Laser stands for “Light amplification by stimulated emission of radiation” and maser stands for
“Microwave amplification by stimulated emission of radiation” [6].Both the lasers and the masers
depend upon stimulated emission discovered by Einstein. The purpose of both the devices is the
generation and amplification of a radiation. But the difference is that lasers are used to produce
photons of high energy either in the ultraviolet region or the visible region. Masers produce
photons of higher wavelength thus the Energy of those photons is low.
When the atoms are excited because of spontaneous emission the average life time is 10-8
sec [6].
The atoms go to high energy state and then emit photon and the life cycle as mentioned is 10-8
sec. When the atoms are in metastable state the life time can become as short as 10-3
sec [6]. This
life time is important for MASER.
Maser is good for generation of coherent long wavelength radiation and it’s amplification but
moving towards short wavelengths with masers is a problem and they are listed below, [7]
For lasers a large number of electromagnetic oscillations are required in the cavity
whereas maser cavity requires only one oscillation.
For lasers especially in the optical region unless the stimulated emission reaches a higher
level it is submerged by the spontaneous emission which is incoherent as well.
Energy differences for masers to generate microwaves are small whereas energy
differences for lasers to generate optical radiation or UV radiation are very high and
comparable to kT.
Tuneable and monochromatic signal generators are used to excite the atoms for the
generation of microwaves but not for the lasers. Untuneable, monochromatic and
broadband radiators are used for the lasers.
16
2. Overview of current technologies to treat toxic material
2.1. Thermal Energy: Incineration and pyrolysis
Pyrolysis is a process in which waste materials are thermally decomposed into gas and solid
phases in the absence of oxygen. Majority of pyrolysis reactions occur at temperature of around
500 °C. [9]
There can be different applications of pyrolysis but the commercially used applications are [9]
Waste to Energy
Carbonization
Soil Remediation
These applications are vital because they convert waster toxic materials into vital products. This
fact is demonstrated by Table 2.1.
Table 2.1: Applications, input materials and products of pyrolysis, [9]
Applications Input toxic waste materials Products by
pyrolysis
1 Carbonization Wooden chips
Organic sludge
Fertilizer
Solid fuel
2 Waste to Energy Municipal solid waste
Waste plastics
Medical waste
Rubber and tires
E-waste
Biomass/wood
Organic sludge (sewage, oil , paper
sludge)
Electrical
Energy
Steam
Black Carbon
Oil
Non-oxidized
metals
3 Soil remediation Contaminated soil (dioxins, oil,
mercury, organics
Cleaned soil
The plants for pyrolysis can be operated both batch as well as continuous mood. There are 5
main steps of batch process which include loading the toxic waste material, heating it up in the
system, pyrolysis, after pyrolysis system is cooled and then the products are unloaded from the
system. Batch process has it’s attraction for the investment cost comparing with continuous
17
pyrolysis units but it requires extensive manual labor so the company’s prefer to have continuous
pyrolysis units. [9]
In continuous pyrolysis unit, there is a rotary kiln that is heated to a temperature of around 400-
600 °C. Absence of oxygen in the kiln is ensured. Toxic waste material is moved in the rotary
kiln where it is heated to generate syngas and flue gas. Syngas is sent to the boiler where it
produces steam. Whereas flue gas is sent to emission control system. The efficiency of pyrolysis
unit heavily depends upon the toxic waste material composition. [9]
Pyrolysis can be used for the treatment of [9]
Biomass
Plastics
Medical waste
Tires
E-waste
Soil
Biomass consists of wood waste, agricultural waste. Pyrolysis is done on these waste products
and the gas which is produced can be directly used for power generation. Generated electricity
depends upon the moisture and biomass type.
1.25 t/h wooden chips (14 MJ/kg) with moisture content nearly 25% generate about 1.2 MWe. [9]
4 t/h of poultry liter nearly 10 MJ/kg generate 2.3 MWe. [9]
As plastic wastes are contaminate most of the times, so their directly recycling is not a possibility
in most of the cases. Plastic wastes contain bio waste, metal, food, beverage packing. So it really
becomes difficult to separate the plastic waste from at the pyrolysis facility. By the pyrolysis of
plastic bags not only energy is generated but oil condensing as well. This oil can either be used
in diesel generators or as heating oil. Automotive shredded Residue (ASR) which consists of
plastics, rubber, glass, wood products, cloth paper, dirt and electrical wiring has higher efficiency
for power generation than municipal solid waste. [9]
18
Generally hospital waste that is sent to the waste deposit facility is incinerated. This hospital
waste consists of pharmaceutical waste, textile, pathological wastes, plastics, polyvinylchloride,
needles etc. But this incineration results in production of carbon monoxide, dioxins. This
incineration of medical waste is banned in California just because of this reason. Pyrolysis is a
better option for the treatment of medical waste but the output entirely depends upon the type of
medical waste. [9]
Doing incineration is not a good option on tiers as 450 kg of toxic gases are produced by burning
just a single ton of tires [9]. Pyrolysis is surely an option but the oil generated through the
pyrolysis of tires has high sulfur content as well as residual content. Therefore the oil produced
through pyrolysis of tires needs further refinement. Carbon black which is physically and
chemically distinct is also a part of this oil. So carbon black, sulfur at the big issues which add to
the cost of oil produced through the pyrolysis of tires. Normally 315 kg/h of oil is produced from
800 kg/h tires pyrolysis. 6.5 MW electricity can be generated through 3 t/h of tires pyrolysis. [9]
Electronic waste is a big problem right now in the world. But printed circuit boards which are
made of ceramics, fiberglass, noble metals and organic resins are not a problem. Soil
contaminated with dioxin, PCB, organic pollutants can be easily cleaned through pyrolysis. [9]
The whole process of incineration is demonstrated by Figure 2.1. [10]
1. Waste deposit area by trucks
2. It’s a hopper and the waste material is moved into it through yellow colored lifters.
3. It’s the incineration unit which gets the waste material from hopper. The temperature of
incineration is around 750 °C
4. It’s the boiler which receives steam produced by incineration and sends it to power
generation facility.
5. Ash content is moved to 5 and from this position ash is passed over electromagnetic
facility in order to separate metal content from it
6. It’s a scrubber which receives flue gases from incineration unit. It is where SO2 and
dioxins are treated.
7. It’s a system to remove fine particles.
8. Chimney
19
Figure 2.1: Incineration process, [10]
European Union has applied strict operation conditions on incineration because of the toxic
emissions produced by the process. These emissions polluted air, water and soil and dangerous
for human health. The conditions include permits, delivery and reception of waste, the operating
conditions, air emissions limit values, water discharges from the cleaning of exhaust gases,
residues, monitoring and surveillance, access to information and public participation,
implementation reports and penalties. [11]
There is a difference between pyrolysis and incineration [9]
During commercial usage, emission of harmful products is much easier to control
comparing with incineration.
The energy required to start up the process is the only energy required for the process in
case of pyrolysis
Pyrolysis does not generate waste water effluent from gas cleaning system.
In pyrolysis the metals obtained are without oxides
The waste treated by pyrolysis can be both, high calorific and low calorific
2.2. Plasma Energy:
Plasma is a mixture of electrons, ions and neutral particles but it’s overall electrically neutral.
Temperature defines the degree ionization of plasma. Higher the temperature higher the number
of electrons lost by the atoms and higher the degree of ionization. When electrical current is
20
passed through the gas, due to electrical resistivity heat is generated which results in creation of
plasma (ionized gas). [12]
Asbestos containing residues can be destroyed through plasma in the presence of argon gas.
Asbestos can be converted into a rocklike structure by plasma. There is a water of crystallization
in asbestos and introducing it to plasma reduces volume by 5% and weight by 70% but that is
only partial treatment. [12]
In France at a commercial facility (INERTAM), high temperature plasma vitrification of
asbestos is carried out in the presence of air. [12]
Tetronics in UK use 1600 °C temperature for asbestos destruction through plasma. They are
successful in destroying asbestos by 100%. [12]
Health care wastes are divided into two types. One which is not dangerous and does not
required special handling. Other type of waste is dangerous as it contains pathogenic
microorganisms, it requires special handling. [12]
Plasma can kill all bacteria and microorganisms because of its high temperature and ultra violet
radiation. Drug structures are also destroyed by plasma.
Technical University in Poland, have destroyed hospital fly ashes. Molten waste was kept at
1500-1600 °C for 30 mins and then air cooled. [12]
Institute of plasma research in India compared plasma technology with other waste treatment
technologies for hospital waste. The waste contained cotton and plastic in a ratio of 2:1. Plasma
destroyed all bacteria but pyrolysis couldn’t. Pyrolysis results contained hydrogen, carbon mono
oxide and lower molecular weight hydro carbons. [12]
Steel making wastes generally consists of stable oxides (calcia, silica, and alumina), oxides
(Iron, chromium, Nickel, Manganese, and Phosphorous), volatile metals (Zinc, lead, Cadmium).
Oxides can be reduced by using reduced plasma. Volatile metals can be collected from the vapor
phase. [12]
Technologies such as PLASMADUST, plasma arc centrifugal technology have been used for the
treatment of steel making wastes. [12]
21
Electroplating on metals is done in order to save them from corrosion. Zinc, Chromium, Nickel
plays a vital role in that. Waste water coming out of electroplating industry contains Zinc,
Chromium, and Nickel. The waste water can be cleaned with the help of plasma with different
gas atmospheres at reduced pressure. After the treatment of waste water, powders can be
collected from the walls of reactor. There elements are present in the forms of ferrite, chromite.
[12]
Aluminum dross is the result of Aluminum reaction with atmosphere as well as entrapped
oxides into the flux which form slag. This dross can be 1-5% of the total melt and my contain
upto 10% Aluminum by weight. Because of the flux used, it becomes toxic and contains fluoride
and chlorides. The dross can be dissolved by thermal plasma. [12]
Thermal plasma treatment of carbonaceous wastes is very efficient by the gasification of the
carbon waste to reduce its weight and volume and result in the production of synthesis gas. [12]
Incineration is not a good technique for chlorine containing wastes. Combination of pyrolysis
and plasma is an efficient way of destroying chlorine containing wastes. It’s because incineration
of Chlorine results in dioxins and furans whereas plasma treatment suppress it. [12]
Plasma is an efficient way of destroying toxic materials but its economic viability is not clear on
large scale. Though different feasibility reports have been presented for many toxic materials. [12]
2.3. Microwave Energy:
The biggest advantage of microwave technology is that, if the process is properly controlled,
uniform heating can be ensured. Instead of heating material, from external source heat is
generated inside the material. So different materials give different response to microwave
technology. The materials which don not absorb microwaves cannot be destroyed by microwave
technology. On the contrary, those materials which absorb microwaves and are called as
dielectrics must possess two properties. [13]
Upon exposure to an external electrical field, there must be very low number of charge
carriers in the material.
Dipole movement must be exhibited by the atoms/molecules of the material.
22
When a dielectric material is placed in an external field, the dipoles realign themselves according
to the external applied filed. When the electromagnetic field is alternating, the dipoles realign
themselves 2.5 billion timers per second. This realignment causes friction and that generates
heat. [13]
Volatile organic compounds can be destroyed using microwave technology. Conversion for
tetrachloroethylene and trichloroethane are 99% effective and they are converted into less
noxious compounds. [14]
In USA, Las Alamos National Laboratory a microwave fluidized bed reactor was made so that
waste of organic compounds can be treated by oxidation reaction. [14]
Soil which contains toluene and xylene can be decontaminated by the use of microwave
technology. It was studied by the researchers in Mississippi University USA. [14]
Microwave technology has been successful in dewatering of low level of nuclear waste. It
reduces the waste volume by 5%. The product obtained by the dewatering of low level nuclear
waste met Canadian Atomic Energy central Board acceptance criteria. [14]
Microwave treatment of Plutonium is a possibility made by Kobe Steel Limited. They
developed a method at Power reactor and Nuclear Fuel development corporation Japan. [14]
University of Florida and Savannah River Technology worked together on microwave
technology to study the waste management. They found out that different electronic
components could be treated by 1-step hybrid heated microwave processes. The reduction in
volume they achieved was significant and was greater than 50%. [14]
Metal components could be separated from the glass using microwave technology. Through
microwave technology they were even able to separate metals like gold and silver and the metals
obtained were in reusable conditions. [14]
Scrap tires can also be treated by microwave technology, it’s an expensive process but
important by-products are formed which may make the destruction of tires through microwave
technology a feasible process. [13]
23
SO2 and NOx have been destroyed through microwave technology as well by using NH3 and
water as reagents. At 1.2 kW 90% destruction efficiency is achieved for SO2 but gaseous mixture
of NOx does not give good efficiency. In case of NOx the reaction rate of destruction is higher
than the rate of destruction. But this condition exists only below 400 W. A combination of
electron beam microwave irradiation is more efficient for the destruction of NOx gaseous
mixture. [13]
Microwaves can give 90% efficiency to clean soil when it comes to the destruction of PCBs and
heavy metals. But often commercial methods can give the destruction efficiency as high as 90%.
[13]
Sewage Sludge volume can be reduced to 80% by using microwave technology. First it dries the
sludge at 200 °C, then to achieve temperature of 900 °C some microwave absorbent material is
inserted in the sludge and it is pyrolysed. [13]
In US, 170 sewage sludge incineration plants are functioning at this time. But they emit
pollutants which include metals, carbon monoxide, NOx, SO2 and unburned hydrocarbons. [13]
24
3. Comparison tables for destruction of selected toxic materials through different technologies Toxic materials in all three states of matter were studied. i.e. solids, liquids and gases.
Solid material studied are Phosphors and Asbestos
Gaseous material studied is NOx (NO, NO2)
Liquid materials studied are
a) Acids
1. Hydrogen Iodide, HI
2. Oxalic Acid, H2C2O4
3. Formic Acid, HCOOH
4. Nitric Acid, HNO3
5. Hydrogen Peroxide, H2O2
6. Acetic Acid, CH3COOH
7. Boric Acid, H3BO3
8. Nucleic Acids
9. Sulfuric Acid, H2SO4
10. Citric Acid, C6H8O7
11. Benzoic Acid, C6H5COOH
12. Yeast Nucleic Acid
13. Hydrogen Bromide, HBr
14. Chromic Acid, H2CrO4
15. Hydrochloric Acid, HCl
b) Bases
1. Sodium bicarbonate, NaHCO3
2. Sodium Carbonate, Na2CO3
3. Ammonia, NH3
4. Barium Hydroxide, Ba(OH)2
5. Potassium Hydroxide, KOH
6. Aluminum Hydroxide, Al(OH)3
7. Magnesium Hydroxide, Mg(OH)2
25
8. Sodium Hydride, NaH
9. Lithium Hydroxide, LiOH
10. Calcium Hydroxide, Ca(OH)2
11. Strontium Hydroxide, Sr(OH)2
12. Sodium Hydroxide, NaOH
13. Nickel Hydroxide, Ni(OH)2
14. Calcium Oxide, CaO
c) Organic Solvents
1. Acetic Acid, CH3COOH
2. Methanol, CH3OH
3. Propanol, CH3CH2CH2OH
4. Triethylamine alane, TEAA
5. Ethanol, CH3CH2OH
6. Isopropanol, (CH3)2CHOH
7. Methylene Chloride, CH2Cl2
8. n-heptane, C7H16
9. toluene, C7H8
10. Propylene carbonate, C4H6O3
11. Alkylamines (propyl amine, diethyl amine, triethylamine)
12. Benzene, C6H6
13. Acetone, (CH3)2CO
14. Methyl tert-butyl ether, C5H12O
15. Formic Acid, HCOOH
16. Chloroform , CHCl3
17. Tetrachloro-ethylene, C2Cl4
18. Diethyl ketone, C5H10O
In the appendix there are tables that show the conventional technologies used to destroy toxic
materials. Different technologies have been written in a tabulated form by considering the factors
as follows:
26
Destruction technology: The technology which is used to destroy the toxic material.
Efficiency: toxic material destroyed divided by the toxic material at the beginning of the
process.
Amount of destruction: The amount of toxic material that has been destroyed
By products: The by-products which are formed after the destruction of the toxic material.
Skilled Labor: It is judged through the machines used in the process.
Dangerous process: It has been decided on the basis of handling the toxic materials
Automatic process: It has been decided on the basis that whether the technology used needs
handling of the toxic material during destruction or not.
Pre-treatment of toxic material before destruction (PTOTMBD): It has been judged on the
fact whether the toxic material needs any pre-treatment before destruction or not.
Pre-treatment of destroying agent before destruction (PTODABD): It he been judged on the
fact whether destroying agent needs any pre-treatment before destroying toxic material or not.
Investment cost: It has been decided upon the equipment and machines used in the destruction
process as well as the analysis
Running cost: It has been decided upon the materials required for the start of destruction
process and as well as analysis once the machines and equipment for the process are already
there
Working area: It has been based on the equipment and machines used in the destruction process
as well as its analysis
Number of Labor: It has been decided on the fact whether the destruction process can be
carried out by a single person or more than one person is required.
Comments: For some technologies there was a need to give some comments at the end, which
are mentioned in comments.
27
4. Molecular dissociation model
In this section a simple mathematical model is developed in order to simulate the destruction of
toxic waste primarily. Obviously the simulation can be extended to the non-toxic materials. The
energy of molecular dissociation is calculated for every chemical formula. This energy value is
then utilized as energy of the Planck equation, which in turn is exploited to find a virtual photon
of such wavelength capable to dissociate the molecule thus destroying it. Then it is assumed that
this photon has an energy which is n-times the energy of a real photon associated to the
wavelength of the selected laser, which is in turn n-times the virtual photon wavelength. So the
value of n is therefore extracted as the ration between the selected laser wavelength and the
virtual wavelength. Basically n is also the number of photons that ideally shall be used to
dissociate the molecules. This value of n is utilized in relation to the value of the number of
photons in a commercially available laser, for example a rather exotic but already realized
Nd:YAG of 100 J per pulse of 10 ns and repetition frequency of 20 Hz. The real total laser
energy found to supply the number of photons necessary to dissociate the toxic molecule under
evaluation is considered to be the sum of the energy at every laser pulse. This is a condition that
should be validated experimentally. Due to budget limitations only the theoretical part has been
developed.
4.1. Solids
4.1.1. Zinc Sulfide, ZnS
Energy required to decompose ZnS [197] is calculated as follows using Hess’s Law
Eqn1 2ZnS(s) + 3O2 (g) → 2ZnO(s) + 2SO2 (g) ΔH= -927.54 kJ
Eqn2 2SO2 (g) + O2 (g) → 2SO3 (g) ΔH= -196.04 kJ
Eqn3 No(s) + SO3 (g) → ZnSO4(s) ΔH= -230.32 kJ
Eqn4 8Zn(s) + S8(s) + 16O2 (g) → 8ZnSO4(s) ΔH= -7808.24 kJ
Reverse Eqn1 x 4 => 8ZnO(s) + 8SO2 (g) → 8ZnS(s) + 12O2 (g) ΔH= 3710.16 kJ
Reverse Eqn3 x 8 => 8ZnSO4(s) → 8ZnO(s) + 8SO3 (g) ΔH= 1842.56 kJ
28
Eqn4 => 8Zn(s) + S8(s) + 16O2 (g) → 8ZnSO4(s) ΔH= -7808.21 kJ
Reverse Eqn2 x 4 => 8SO3 (g) → 8SO2 (g) + 4O2 (g) ΔH= 784.16 kJ
8Zn(s) + S8(s) → 8ZnS(s) ΔH= -1471.12 kJ
ZnS(s) → Zn(s) + 1/8S8(s) ΔH= 183.89 kJ/mol [197]
According to Max Planck Energy equation
Total energy is given by
λL of laser to destroy toxic material
Comparing the two ET equations
29
To find out the material destroyed in kilogram per hour, following mathematical calculations
were applied on all toxic materials that follow. The results are shown in the tabulated form at the
end of the dissociation energy calculations. The steps for ZnS are shown below.
λT calculations
Number of photons to destroy 1 mole of toxic material
Energy of one photon of the selected laser
Number of photons in laser beam
Number of pulses to destroy 1 mole of toxic material
Number of pulses generated in one second
Time to generate the pulse that is sufficient enough to destroy 1 mole of toxic
material
Amount of toxic material destroyed in kg/hrs.
λT calculations
Putting the values of planks constant, speed of light and the energy calculated through Hess’s
law to destroy ZnS can be calculated for each mole
Number of photons to destroy 1 mole of toxic material
As derived about the number of photons to destroy 1 mole of toxic material can be calculated
through following relation
30
Energy of one photon of the selected laser
This case shows the usage of gas dynamic laser developed by Professor Apollonov
Putting the values of plank’s constant, speed of light and value of wavelength of gas dynamic
laser developed by Professor Apollonvo, the energy of one photon of the laser can be calculated
as follows
Number of photons in laser beam
Number of photons in the 2.86 J Laser beam of Infra-Red CO2 is calculated as
Putting the values of Infra-Red CO2 laser in the above relation, number of photons in laser beam
is calculated
Number of pulses to destroy 1 mole of toxic material
Putting the values of number of photons to destroy 1 mole of ZnS as calculated above and
putting the value of number of photons in 1 laser beam we can have following result
Number of pulses generated in one second
Number of pulses generated in one second for gas dynamic laser developed by Professor
Apollonov is 350,000.
31
Time to generate the pulse that is sufficient enough to destroy 1 mole of toxic material
Putting the above calculated values in the mathematical relation gives the value of time to
generate the pulse that is sufficient enough to destroy 1 mole of toxic material
Amount of toxic material destroyed in kg/hrs.
Molar Mass of ZnS= 97.474
Mass of ZnS in kg= 0.097474 kg
The above calculations have been repeated for all the toxic materials and written in tabulated
form at the end of the equations
4.2. Gases
4.2.1. NO
Energy required to decompose NO [198] is calculated as follows using Hess’s Law
Eqn1 2NH3 (g) → N2 (g) + 3H2 (g) ΔH= 91.8 kJ
Eqn2 2H2 (g) + O2 (g) → 2H2O (g) ΔH= -483.6 kJ
Eqn3 4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g) ΔH= -1628.2 kJ
Eqn1 x 2=> 6H2 (g) + 2N2 (g) → 4NH3 (g) ΔH= -183.6 kJ
32
Eqn2 x 3=> 6H2O (g) → 6H2 (g) + 3O2 (g) ΔH= 1450.8 kJ
Eqn3=> 4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g) ΔH= -1628.2 kJ
2N2 (g) + 2O2 (g) → 4NO (g) ΔH= -361 kJ
NO (g) → 1/2N2 (g) + 1/2O2 (g) ΔH= 90.25 kJ/mol [198]
4.2.2. NO2
Energy required to decompose NO2 [199] is calculated as follows using Hess’s Law
Eqn1 N2 (g) + 2O2 (g) → N2O4 (g) ΔH= -9.16 kJ
Eqn2 N2O4 (g) → 2NO2 (g) ΔH= -57.2 kJ
Eqn1=> N2 (g) + 2O2 (g) → N2O4 (g) ΔH= -9.16 kJ
Eqn2=> N2O4 (g) → 2NO2 (g) ΔH= -57.2 kJ
N2 (g) + 2O2 (g) → 2NO2 (g) ΔH= -66.36 kJ
NO2 (g) → 1/2N2 (g) + O2 (g) ΔH= 33.13 kJ/mol [199]
The mathematical model for liquids is in the appendix.
4.3. Calculations for number of photons to destroy toxic materials
There are four lasers which are under consideration as shown in the following table.
Decomposition energies, wavelength required to decompose the toxic material, wavelength of
the lasers and the energy associated with one of photon of each laser is used to calculate the
number of photons required to destroy the toxic material. Table 4.3.1 shows the wavelength and
energy of one photon associated with each laser.
33
Table 4.3.1: Wavelength and energy of one photon for four different types of lasers [200]
Lasers Wavlength (nm) Wavelenght (m)
Energy of one
photon (J)
Infrad Red CO2 Laser 10064 0,000010064 1,97379E-20
Nd:YAG 1064 0,000001064 1,86694E-19
Green Laser,frequency doubled Nd:YAG 532 0,000000532 3,73388E-19
UV Laser, frequency tripled Nd:YAG 266 0,000000266 7,46776E-19
Number of photons to destroy one mole of toxic liquid is demonstrated by the equation
Table 4.3.2 the number of photons required by each laser in above to destroy toxic solid (ZnS).
Table 4.3.2: No of photons to destroy 1 mole of toxic solids by 4 different lasers
Sr.No
Toxic
solids
Decomposition
Energy (J/mol)
No.of photons to
destroy on mole of
toxic solid by Infra
Red CO2
laser,n1/mol
No.of photons to
destroy one mole
of toxic solid by
Nd:YAG
laser,n2/mol
No.of photons
to destroy one
mole of toxic
solid by Green
laser,n3/mol
No.of photons
to destroy one
mole of toxic
solid by UV
laser,n4/mol
1 ZnS 183890 9,31658E+24 9,8498E+23 4,9249E+23 2,46245E+23
Table 4.3.3 demonstrates the number of photons required by each laser shown in Table4.3.1 to
destroy toxic gases (NO, NO2).
Table 4.3.3: No of photons to destroy 1 mole of toxic gases by 4 different lasers
Sr.No
Toxic
Gases
Decomposition
Energy (J/mol)
No.of photons to
destroy one mole
of toxic gas by
Infra Red CO2
Laser,n1/mol
No. of photons to
destroy on mole of
toxic gas by
Nd:YAG
laser,n2/mol
No.of photons
to destroy on
mole of toxic
gas by Green
laser,n3/mol
No.of photons
to destroy on
mole of toxic
gas by UV
laser,n4/mol
1 NO 90250 4,57242E+24 4,83411E+23 2,41706E+23 1,20853E+23
2 NO2 33130 1,67849E+24 1,77456E+23 8,8728E+22 4,4364E+22
34
Table 4.3.4 demonstrates the number of photons required by each laser shown in Table 4.3.1 to
destroy liquids
Table 4.3.4: No of photons to destroy 1 mole of toxic liquids by 4 different lasers
Sr.
No Toxic Liquids
Decompo
sition
Energy
(J/mol)
No.of photons to
destroy one mole
of toxic liquid by
Infra Red CO2
laser,n1/mol
No.of photons to
destroy one mole
of toxic liquid by
Nd:YAG
laser,n2/mol
No. of photons
to destroy one
mole of toxic
liquid by Green
Laser,n3/mol
No.of photons
to destroy one
mole of toxic
liquid by UV
laser, n4/mol
1 Hydrogen Iodide -26000 -1,31726E+24 -1,39265E+23 -6,96326E+22 -3,48163E+22
2 Oxalic Acid 252620 1,27987E+25 1,35312E+24 6,76561E+23 3,38281E+23
3 Formic Acid 40531 2,05346E+24 2,17098E+23 1,08549E+23 5,42746E+22
4 Nitric Acid 174000 8,81552E+24 9,32006E+23 4,66003E+23 2,33002E+23
5 Hydrogen peroxide 187600 9,50454E+24 1,00485E+24 5,02426E+23 2,51213E+23
6 Acetic Acid 485000 2,4572E+25 2,59783E+24 1,29892E+24 6,49458E+23
7 Boric Acid 7195 3,64527E+23 3,8539E+22 1,92695E+22 9,63475E+21
8 Sulfuric Acid 72000 3,6478E+24 3,85658E+23 1,92829E+23 9,64144E+22
9 Citric Acid 1384000 7,01188E+25 7,4132E+24 3,7066E+24 1,8533E+24
10 Benzoic Acid 385070 1,95091E+25 2,06257E+24 1,03129E+24 5,15643E+23
11 Hydrogen Bromide 36400 1,84417E+24 1,94971E+23 9,74857E+22 4,87428E+22
12 Hydrochloric Acid 92330 4,6778E+24 4,94552E+23 2,47276E+23 1,23638E+23
13 Sodium bicarbonate 91630 4,64233E+24 4,90803E+23 2,45401E+23 1,22701E+23
14 Sodium bicarbonate 950800 4,81712E+25 5,09282E+24 2,54641E+24 1,27321E+24
15 Sodium carbonate 1130680 5,72846E+25 6,05633E+24 3,02816E+24 1,51408E+24
16 Ammonia 46050 2,33307E+24 2,4666E+23 1,2333E+23 6,16651E+22
17 Barium Hydroxide -512000 -2,59399E+25 -2,74245E+24 -1,37123E+24 -6,85614E+23
18 Potassium Hydroxide 487000 2,46733E+25 2,60855E+24 1,30427E+24 6,52136E+23
19 Aluminium Hydroxide 1274900 6,45914E+25 6,82882E+24 3,41441E+24 1,7072E+24
20 Magnesium Hydroxide 924750 4,68514E+25 4,95329E+24 2,47665E+24 1,23832E+24
21 Sodium Hydride 78000 3,95178E+24 4,17796E+23 2,08898E+23 1,04449E+23
22 Lithium Hydroxide 485000 2,4572E+25 2,59783E+24 1,29892E+24 6,49458E+23
23 Calcium Hydroxide 985000 4,99039E+25 5,27601E+24 2,63801E+24 1,319E+24
24 Strontium Hydroxide -506000 -2,56359E+25 -2,71032E+24 -1,35516E+24 -6,77579E+23
25 Sodium Hydroxide 425130 2,15387E+25 2,27715E+24 1,13857E+24 5,69287E+23
26 Calcium Oxide 635000 3,21716E+25 3,40129E+24 1,70064E+24 8,50322E+23
27 Acetic Acid 485000 2,4572E+25 2,59783E+24 1,29892E+24 6,49458E+23
28 Methanol 240000 1,21593E+25 1,28553E+24 6,42763E+23 3,21381E+23
29 Propanol 318730 1,61481E+25 1,70723E+24 8,53616E+23 4,26808E+23
30 Ethanol 275420 1,39538E+25 1,47525E+24 7,37624E+23 3,68812E+23
31 Isopropanol 303730 1,53881E+25 1,62689E+24 8,13443E+23 4,06722E+23
32 Methylene Chloride 91500 4,63575E+24 4,90107E+23 2,45053E+23 1,22527E+23
33 n-heptane 190970 9,67528E+24 1,0229E+24 5,11452E+23 2,55726E+23
34 Toulene -48130 -2,43845E+24 -2,57801E+23 -1,28901E+23 -6,44504E+22
35 Propylene carbonate 624340 3,16315E+25 3,34419E+24 1,67209E+24 8,36047E+23
36 Benzene 49000 2,48253E+24 2,62461E+23 1,31231E+23 6,56154E+22
37 Acetone 248120 1,25707E+25 1,32902E+24 6,6451E+23 3,32255E+23
38 methly tert-butyl ether 313600 1,58882E+25 1,67975E+24 8,39877E+23 4,19938E+23
39 Formic Acid 405310 2,05346E+25 2,17098E+24 1,08549E+24 5,42746E+23
40 Chloroform 134470 6,81277E+24 7,20269E+23 3,60135E+23 1,80067E+23
41 tetrachloro-ethylene 10760 5,45143E+23 5,76344E+22 2,88172E+22 1,44086E+22
35
Figure 4.3.1 to figure 4.3.5 demonstrate the graphs drawn between numbers of photons required
to destroy one mole of toxic material for four different lasers as mentioned above, against the
type of material.
Figure 4.3.1: Number of photons to destroy one mole of toxic solid by lasers
Figure 4.3.2: Number of photons to destroy one mole of toxic gas by lasers
0
2E+24
4E+24
6E+24
8E+24
1E+25
ZnS
9,31658E+24
9,8498E+23 4,9249E+23
2,46245E+23
No. of photons
No. of photons to destroy one mole of toxic solid by lasers
IR CO2 Laser Nd:YAG Laser Green Laser UV Laser
0
1E+24
2E+24
3E+24
4E+24
5E+24
NO
NO2
4,57242E+24
1,67849E+24 4,83411E+23
1,77456E+23 2,41706E+23
8,8728E+22 1,20853E+23
4,4364E+22
No of photons
Type of gas
No. of photons to destroy one mole of toxic gas by lasers
IR CO2 Laser Nd:YAG Laser Green Laser UV Laser
36
Figure 4.3.3: Number of photons to destroy one mole of acids by lasers
Figure 4.3.4: Number of photons to destroy one mole of base by laser
37
Figure 4.3.5: Number of photons to destroy one mole of organic solvent by laser
At present there is no laser available with the pulse rate and the very demanding specifications
imposed by the dissociation energies calculated. One of the biggest limits is the pulse frequency
rate. Only the Gas Dynamic Laser developed by Professor Apollonov producing 100 KW of
peak power (2.86 J) with pulses of 5 ns at prf of 350 KHz is the solution to be utilized to
demolish the toxic materials evaluated. The other laser sources may be utilized exploiting laser
plasma interaction and not molecular dissociation.
4.4. Material destroyed rate by CO2 Gas Dynamic Laser
CO2 Gas Dynamic Laser developed by Apollonov [236] is the ideal laser and the calculations are
made using its specifications
Wavelength of 10640 nm
1 MW peak power (It can deliver 250 MW in 3 seconds)
2.86 J @ 5 ns pulsed width
prf 350 kHz.
The procedure used to calculate the values written in the tables is elaborated under heading 4.1.1.
38
4.4.1. Solids
Table 4.4.1.1 demonstrates the results obtained by mathematical calculations as mentioned in
section 4.1.1, for ZnS. Values of CO2 Gas Dynamic Laser developed by Apollonov are used.
Table 4.4.1.1
Planks
Constant 6,63E-34
Speed of
Light 299792458
Infrad Red
CO2 Laser
λL(m) 1,06E-05
Sr.
No
Toxic
solids
Decompositio
n Energy
(J/mol) λt=hc/E
No of
photons to
destroy toxic
material
Energy of
one photon
of Infra Red
CO2, Laser
No.of photons
in 2.86J Laser
beam of Infra
Red CO2,n
No.of pulses
to destroy
toxic
material
1 ZnS 183890 1,08E-30 9,85E+24 1,87E-20 1,53E+20 6,43E+04
By following the procedure mentioned in section 4.1.1, Table 4.4.1.2 demonstrates the results of
material destroyed in kg/hr for ZnS.
Table 4.4.1.2
Sr.
No
Number of pulses
generated in 1 sec
Time to generate
required pulses to
destroy one mole of
toxic mat,sec
Molar
Mass
Mass in
kg
Material
detroyed
, kg/sec
Material
destroye
d, kg/hr
1 350000 1,84E-01 97,474 0,097474 5,31E-01 1,91E+03
Amount of ZnS destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as
calculated above is demonstrated in Figure 4.4.1.1 for laser energy of 2.86 J.
39
0,00E+00
5,00E+02
1,00E+03
1,50E+03
2,00E+03
ZnS
1,91E+03
kg/hr
ZnS destroyed by 2.86 J Laser
Figure 4.4.1.1: Destruction of ZnS through a laser of energy 2.86 J
4.4.2. Gases
Table 4.4.2.1 demonstrates the results obtained by mathematical calculations as mentioned
in section 4.1.1 for gases. Values of CO2 Gas Dynamic Laser developed by Apollonov are
used.
Table 4.4.2.1
Planks
Constant 6,63E-34
Ligh
Speed 299792458
Infrad Red CO2
Laser λL(m) 1,06E-05
Sr.
No
Toxic
Gases
Decomposition
Energy (J/mol) λt=hc/E
No of photons
to destroy toxic
material
Energy of one
photon of Infra
Red CO2, Laser
No.of photons in
2.86J Laser beam
of Infra Red CO2,n
No.of pulses
to destroy
toxic material
1 NO 90250 2,20E-30 4,83E+24 1,87E-20 1,53E+20 3,16E+04
2 NO2 33130 6,00E-30 1,77E+24 1,87E-20 1,53E+20 1,16E+04
Table 4.4.2.2 demonstrates the material destroyed in kg/hr for gases, by following the procedure
mentioned in section 4.1.1.
40
Table 4.4.2.2
Sr.
No
Number of
pulses
generated
in 1 sec
Time to generate
required pulses to
destroy one mole
of toxic mat,sec
Molar
Mass
Mass,
kg
Material
detroyed,
kg/sec
Material
destroyed,
kg/hr
Dens
ity
Material
destoyed
m3/hr
1 350000 9,02E-02 30 0,03 3,33E-01 1,20E+03 1270 9,43E-01
2 350000 3,31E-02 46 0,046 1,39E+00 5,00E+03 2620 1,91E+00
Amount of gases destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as
calculated above is demonstrated in a graphical form in the figure 4.4.2.1 for the laser of energy
2.86 J.
Figure 4.4.2.1: Nitrogen oxide destruction through lasers of energy 2.865 J
4.4.3. Liquids
Table 4.4.3.1 demonstrates the results obtained by mathematical calculations as mentioned in
section 4.1.1, for liquids. Values of CO2 Gas Dynamic Laser developed by Apollonov are used.
0,00E+00
5,00E-01
1,00E+00
1,50E+00
2,00E+00
NO NO2
9,43E-01
1,91E+00
m3/hr
Gases destruction by 2.865 J Laser
41
Table 4.4.3.1
Planks
Constant 6,63E-34
Speed of
Light 299792458
Infrad Red CO2
Laser λL(m) 1,06E-05
Sr.
No
Toxic
Liquids
Decomposition
Energy (J/mol) λt=hc/E
No of photons
to destroy
toxic material
Energy of 1
photon of Infra
Red CO2, Laser
No.of photons in
2.86J Laser beam
of Infra Red
CO2,n
No.of
pulses to
destroy
toxic
1 HI 26000 7,64E-30 1,39E+24 1,87E-20 1,53E+20 9,09E+03
2 H2C2O4 252620 7,86E-31 1,35E+25 1,87E-20 1,53E+20 8,83E+04
3 HCOOH 405310 4,90E-31 2,17E+25 1,87E-20 1,53E+20 1,42E+05
4 HNO3 174000 1,14E-30 9,32E+24 1,87E-20 1,53E+20 6,08E+04
5 H2O2 187600 1,06E-30 1,00E+25 1,87E-20 1,53E+20 6,56E+04
6 CH3COOH 485000 4,10E-31 2,60E+25 1,87E-20 1,53E+20 1,70E+05
7 H3BO3 7195 2,76E-29 3,85E+23 1,87E-20 1,53E+20 2,52E+03
8 H2SO4 72000 2,76E-30 3,86E+24 1,87E-20 1,53E+20 2,52E+04
9 C6H8O7 1384000 1,44E-31 7,41E+25 1,87E-20 1,53E+20 4,84E+05
10 C6H5COOH 385070 5,16E-31 2,06E+25 1,87E-20 1,53E+20 1,35E+05
11 HBr 36400 5,46E-30 1,95E+24 1,87E-20 1,53E+20 1,27E+04
12 HCl 92330 2,15E-30 4,95E+24 1,87E-20 1,53E+20 3,23E+04
13 NaHCO3 91630 2,17E-30 4,91E+24 1,87E-20 1,53E+20 3,20E+04
14 NaHCO3 950800 2,09E-31 5,09E+25 1,87E-20 1,53E+20 3,32E+05
15 Na2CO3 1130680 1,76E-31 6,06E+25 1,87E-20 1,53E+20 3,95E+05
16 NH3 46050 4,31E-30 2,47E+24 1,87E-20 1,53E+20 1,61E+04
17 Ba(OH)2 512000 3,88E-31 2,74E+25 1,87E-20 1,53E+20 1,79E+05
18 KOH 487000 4,08E-31 2,61E+25 1,87E-20 1,53E+20 1,70E+05
19 Al(OH)3 1274900 1,56E-31 6,83E+25 1,87E-20 1,53E+20 4,46E+05
20 Mg(OH)2 924750 2,15E-31 4,95E+25 1,87E-20 1,53E+20 3,23E+05
21 NaH 78000 2,55E-30 4,18E+24 1,87E-20 1,53E+20 2,73E+04
22 LiOH 485000 4,10E-31 2,60E+25 1,87E-20 1,53E+20 1,70E+05
23 Ca(OH)2 985000 2,02E-31 5,28E+25 1,87E-20 1,53E+20 3,44E+05
24 Sr(OH)2 506000 3,93E-31 2,71E+25 1,87E-20 1,53E+20 1,77E+05
25 NaOH 425130 4,67E-31 2,28E+25 1,87E-20 1,53E+20 1,49E+05
26 CaO 635000 3,13E-31 3,40E+25 1,87E-20 1,53E+20 2,22E+05
27 CH3COOH 485000 4,10E-31 2,60E+25 1,87E-20 1,53E+20 1,70E+05
28 CH3OH 240000 8,28E-31 1,29E+25 1,87E-20 1,53E+20 8,39E+04
29CH3CH2CH2OH 318730 6,23E-31 1,71E+25 1,87E-20 1,53E+20 1,11E+05
30 CH3CH2OH 275420 7,21E-31 1,48E+25 1,87E-20 1,53E+20 9,63E+04
31(CH3)2CHOH 303730 6,54E-31 1,63E+25 1,87E-20 1,53E+20 1,06E+05
32 CH2Cl2 91500 2,17E-30 4,90E+24 1,87E-20 1,53E+20 3,20E+04
33 C7H16 190970 1,04E-30 1,02E+25 1,87E-20 1,53E+20 6,68E+04
34 C7H8 48130 4,13E-30 2,58E+24 1,87E-20 1,53E+20 1,68E+04
35 C4H6O3 624340 3,18E-31 3,34E+25 1,87E-20 1,53E+20 2,18E+05
36 C6H6 49000 4,05E-30 2,62E+24 1,87E-20 1,53E+20 1,71E+04
37 (CH3)2CO 248120 8,01E-31 1,33E+25 1,87E-20 1,53E+20 8,68E+04
38 C5H12O 313600 6,33E-31 1,68E+25 1,87E-20 1,53E+20 1,10E+05
39 HCOOH 405310 4,90E-31 2,17E+25 1,87E-20 1,53E+20 1,42E+05
40 CHCl3 134470 1,48E-30 7,20E+24 1,87E-20 1,53E+20 4,70E+04
41 C2Cl4 10760 1,85E-29 5,76E+23 1,87E-20 1,53E+20 3,76E+03
42
By following the procedure mentioned in section 4.1.1, table 4.4.3.2 demonstrates the results of
material destroyed in kg/hr for liquids.
Table 4.4.3.2
Sr.
No
Number of
pulses
generated
in 1 sec
Time to generate
required pulses to
destroy one mole
of toxic mat,sec
Molar
Mass
Mass,
kg
Material
detroyed,
kg/sec
Material
destroye
d, kg/hr
Dens
ity
Material
destoyed
m3/hr
1 350000 2,60E-02 128 0,128 4,93E+00 1,77E+04 2850 6,22E+00
2 350000 2,52E-01 90 0,09 3,57E-01 1,28E+03 1900 6,76E-01
3 350000 4,05E-01 46 0,046 1,14E-01 4,09E+02 1220 3,35E-01
4 350000 1,74E-01 63 0,063 3,62E-01 1,30E+03 1510 8,64E-01
5 350000 1,87E-01 34 0,034 1,81E-01 6,53E+02 1450 4,50E-01
6 350000 4,85E-01 60 0,06 1,24E-01 4,46E+02 1050 4,25E-01
7 350000 7,19E-03 62 0,062 8,63E+00 3,11E+04 1440 2,16E+01
8 350000 7,19E-02 98 0,098 1,36E+00 4,90E+03 1840 2,67E+00
9 350000 1,38E+00 192 0,192 1,39E-01 5,00E+02 1665 3,00E-01
10 350000 3,85E-01 122 0,122 3,17E-01 1,14E+03 1270 8,99E-01
11 350000 3,64E-02 81 0,081 2,23E+00 8,02E+03 1490 5,38E+00
12 350000 9,22E-02 36 0,036 3,90E-01 1,41E+03 1490 9,43E-01
13 350000 9,15E-02 84 0,084 9,18E-01 3,30E+03 2200 1,50E+00
14 350000 9,50E-01 84 0,084 8,84E-02 3,18E+02 2200 1,45E-01
15 350000 1,13E+00 106 0,106 9,38E-02 3,38E+02 2540 1,33E-01
16 350000 4,60E-02 17 0,017 3,70E-01 1,33E+03 682 1,95E+00
17 350000 5,11E-01 171 0,171 3,34E-01 1,20E+03 3743 3,22E-01
18 350000 4,87E-01 56 0,056 1,15E-01 4,14E+02 2044 2,03E-01
19 350000 1,27E+00 78 0,078 6,12E-02 2,20E+02 2420 9,11E-02
20 350000 9,24E-01 58 0,058 6,28E-02 2,26E+02 2340 9,66E-02
21 350000 7,79E-02 24 0,024 3,08E-01 1,11E+03 1400 7,92E-01
22 350000 4,85E-01 24 0,024 4,95E-02 1,78E+02 1460 1,22E-01
23 350000 9,84E-01 74 0,074 7,52E-02 2,71E+02 2211 1,22E-01
24 350000 5,05E-01 122 0,122 2,41E-01 8,69E+02 3625 2,40E-01
25 350000 4,25E-01 40 0,04 9,42E-02 3,39E+02 2130 1,59E-01
26 350000 6,34E-01 56 0,056 8,83E-02 3,18E+02 3350 9,49E-02
27 350000 4,85E-01 60 0,06 1,24E-01 4,46E+02 1050 4,25E-01
28 350000 2,40E-01 32 0,032 1,33E-01 4,80E+02 792 6,07E-01
29 350000 3,18E-01 60 0,06 1,88E-01 6,78E+02 803 8,45E-01
30 350000 2,75E-01 46 0,046 1,67E-01 6,02E+02 789 7,63E-01
31 350000 3,03E-01 60 0,06 1,98E-01 7,12E+02 786 9,06E-01
32 350000 9,14E-02 85 0,085 9,30E-01 3,35E+03 1330 2,52E+00
33 350000 1,91E-01 100 0,1 5,24E-01 1,89E+03 684 2,76E+00
34 350000 4,81E-02 92 0,092 1,91E+00 6,89E+03 867 7,94E+00
35 350000 6,24E-01 102 0,102 1,64E-01 5,89E+02 1205 4,89E-01
36 350000 4,90E-02 78 0,078 1,59E+00 5,74E+03 876 6,55E+00
37 350000 2,48E-01 58 0,058 2,34E-01 8,42E+02 791 1,06E+00
38 350000 3,13E-01 88 0,088 2,81E-01 1,01E+03 740 1,37E+00
39 350000 4,05E-01 46 0,046 1,14E-01 4,09E+02 1220 3,35E-01
40 350000 1,34E-01 119 0,119 8,86E-01 3,19E+03 1483 2,15E+00
41 350000 1,07E-02 166 0,166 1,54E+01 5,56E+04 1620 3,43E+01
43
Amount of acids destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as
calculated above is demonstrated in figure 4.4.3.1 in a graphical form for the laser of energy 2.86
J.
Figure 4.4.3.1: Destruction of acids by 2.86J Laser
Amount of bases destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as
calculated above is demonstrated in figure 4.4.3.2 in a graphical form for the laser of energy 2.86
J.
Figure 4.4.3.2: Destruction of bases through a laser of energy 2.86J
6,22E+00
6,76E-01 3,35E-01
8,64E-01 4,50E-01
4,25E-01
2,16E+01
2,67E+00
3,00E-01
8,99E-01
5,38E+00
9,43E-01
0,00E+00
5,00E+00
1,00E+01
1,50E+01
2,00E+01
2,50E+01
m3/hr
Acids destroyed by 2.86 J Laser
1,50E+00
1,45E-01
1,33E-01
1,95E+00
3,22E-01
2,03E-01
9,11E-02
9,66E-02
7,92E-01
1,22E-01
1,22E-01
2,40E-01
1,59E-01
9,49E-02
0,00E+00
5,00E-01
1,00E+00
1,50E+00
2,00E+00
2,50E+00
m3/hr
Bases destroyed by 2.86 J Laser
44
Amount of organic solvents destroyed per hour using CO2 Gas Dynamic Laser developed by
Apollonov as calculated above is demonstrated in figure 4.4.3.3 in a graphical form for the laser
of energy 2.86 J.
Figure 4.4.3.3: Destruction of organic solvents through a laser of energy 2.86 J
The above calculations were made with a laser of 286.5 J Laser and the values obtained are
shown in the following graphs. They showed an increasing trend with increasing the input
energy.
Amount of acids destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as
calculated above is demonstrated in figure 4.4.3.4 in a graphical form for the laser of energy
286.5 J.
4,25E-01 6,07E-01
8,45E-01
7,63E-01
9,06E-01 2,52E+00
2,76E+00
7,94E+00
4,89E-01
6,55E+00
1,06E+00
1,37E+00
3,35E-01 2,15E+00
3,43E+01
0,00E+00
5,00E+00
1,00E+01
1,50E+01
2,00E+01
2,50E+01
3,00E+01
3,50E+01
4,00E+01
m3/hr
Organic Solvents destoyed by 2.86 J Laser
45
Figure 4.4.3.4: Destruction of acids through laser of energy 286.5J
Amount of bases destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as
calculated above is demonstrated in figure 4.4.3.5 in a graphical form for the laser of energy
286.5 J.
Figure 4.4.3.5: Destruction of bases through laser of energy 286.5J
6,22E+02
6,75E+01 3,35E+01
8,63E+01
4,50E+01
4,24E+01
2,15E+03
2,66E+02
3,00E+01
8,98E+01
5,38E+02
9,42E+01
0,00E+00
5,00E+02
1,00E+03
1,50E+03
2,00E+03
2,50E+03
m3/hr
Acids destroyed by 286.5 J Laser
1,50E+02
1,45E+01
1,33E+01
1,95E+02
3,21E+01
2,03E+01 9,10E+00
9,65E+00
7,91E+01
1,22E+01
1,22E+01
2,39E+01
1,59E+01
9,48E+00
0,00E+00
5,00E+01
1,00E+02
1,50E+02
2,00E+02
2,50E+02
m3/hr
Bases destroyed by 286.5 J Laser
46
Amount of organic solvents destroyed per hour using CO2 Gas Dynamic Laser developed by
Apollonov as calculated above is demonstrated in figure 4.4.3.6 for the laser of energy 286.5 J.
Figure 4.4.3.6: Destruction of organic solvents through laser of energy 286.5J
4,24E+01
6,06E+01
8,44E+01
7,62E+01 9,05E+01
2,51E+02 2,76E+02
7,94E+02
4,88E+01
6,54E+02
1,06E+02
1,37E+02
3,35E+01
2,15E+02
3,43E+03
0,00E+00
5,00E+02
1,00E+03
1,50E+03
2,00E+03
2,50E+03
3,00E+03
3,50E+03
4,00E+03
m3/hr
Organic solvents destroyed by 286.5 J Laser
47
5. Plasma exploitation
In this section we are interested to model, investigate and evaluate the rate of transformation into
plasma of each of the most common and dangerous toxic materials. The list of those toxic
materials has been provided by AMIAT, Torino, Italy. This investigation is useful to dimension
the experimental setup in order to realize a table-top demonstrator. Therefore the laser sources
considered in the present simulation are comparatively small respect those which will be utilized
in reality. In order to find the most suitable material to conduct the experiment and also to test
the simulation model, calculations were carried for each of the listed toxic materials (list
supplied by the Director general of AMIAT, Torino, Italy. The purpose was to identify the most
suitable material for preliminary experiments. Once the table-top prototype will be developed
and the simulation model verified calculations will be made utilizing the selected laser source.
Determining the closest values of the destruction rates (measured in kg/s) for each material will
enable to develop a grid of comparison between the proposed laser waste destruction method and
the methods with conventional technologies presently in use to destroy the same types of toxic
materials.
The laser beam aimed at the toxic material vaporizes it and then transforms the vapor into
plasma. Increasing the exposure of the vapor to the laser beam will transform it into a hot
plasma. It is quite obvious that for plasma generation, laser beam fluence [237- 238] must be
greater than vaporization threshold [237, 239]. So first the laser beam will transform toxic
material into vapors and then plasma [237], finally the addition of a suitable catalyst will turn the
hot plasma into a hot, high pressure inert gas.
The mathematical relation for the power density in order to achieve vaporization threshold is
given by following relation [237].
[ ( ) ]√ ⁄
Where [237]
Sv = Power density
48
3 values used are fixed while the others vary from material to material. They are listed below
tp = pulse duration of laser i.e. pulse width. In the calculations it’s fixed as 5 ns. Its range varies
from 500 ps to 10 ns
α = Coefficient of absorption of the material at the specific laser wavelength and it is
dimensionless. Its range varies from 0.01 to 0.3 but in this case fixed value of 0.1 is used.
To = 300 K
The variable values are as follows and depend upon the toxic material
ρ = Density of toxic material in kg/m3
Tv = Vaporization temperature of the targeted toxic material
D = Thermal diffusivity measured in m2/s
(k=thermal conductivity)
Lm = Heat of fusion J/kg
C = Heat Capacity in J/kg K
All the values for all the materials are not available on the internet. So there were problems in
finding vaporization temperature and thermal diffusivity of some materials. So in some cases the
thermal diffusivities and vaporization temperatures are mentioned for the element of the material
which has high molar mass.
Example for ZnS is shown below and then the results of other materials are presented in tabulate
form.
The values of ZnS are
ρ = 4090 kg/m3
Tv = 1458 K; Melting point is written, vaporization temperature hasn’t been determined yet
D = 4.14*10-5
m2/s; thermal diffusivity of Zn is listed. (Thermal diffusivity of most of the
materials is not known so the thermal diffusivity of heavier element is used in those cases)
49
Lm = 2099021
C = 515 J/kg-K
Putting these values in the following equation [237]
[ ( ) ]√ ⁄
If we have a Nd:YAG laser with 5 ns pulse and 10 J energy we will have a peak power of
10 J/5*10-9
=2.0*109 W, thus the beam area will be
2*109 W/1.012x10
10 = 0.19 m
2 ~ 0.2 m
2 with a beam spot diameter of 0.5 m.
With a Nd:YAG laser of 10 J @ 5 ns pulse width we can vaporize a surface of 0.2 m2 of ZnS
Energy deposited per pulse can be calculated with the help of following relation [237]
Mass vaporized per pulse can be calculated from the following relation [237]
√
√
The mass vaporized in one minute of laser action depends on the prf of the laser, for example 10
J laser may have a 5 Hz prf, from the period T we can calculate the number of pulses in one
minute and that is
Np = 60 s * 5 Hz = 30 thus the vaporization interaction time is ty is Np * tp = 30*5*10-9
= 0.15*
10-6
= 0.15 µs, thus total mass evaporated and transformed in one minute of laser operation is
given by [237]
√
50
√
All the materials have been calculated in the same way and the results are expressed in the
tabulated form.
5.1. Solids
Table 5.1.1 demonstrates the data, required in order to find mass evaporated and transformed for
ZnS.
Table 5.1.1: Data table for Solids (ZnS)
Sr.No Toxic solids
Density
(kg/m3)
Vaporization
temperature
Tv,K
Thermal
diffusivity
, D,m2/s
Heat of
fusion,Lm,
J/kg
Heat
Capacity,
C,J/kgK
1 ZnS 4090 1458 4.14E-5 2099021 515
Power density calculations for ZnS are demonstrated in Table 5.1.2.
Table 5.1.2: Power density calculations for ZnS
Sr.No Toxic solids
Density
(kg/m3)
Vaporizat
ion
temperat
ure Tv,K
Thermal
diffusivity
, D,m2/s
Heat of
fusion,Lm
, J/kg Heat Capacity,C,J/kgK
Power
Density
1 ZnS 4090 1458 4,14E-05 2099021 515 7,836E+12
Power Density
Energy deposited per pulse is demonstrated in Table 5.1.3 using the result of power density.
Table 5.1.3: Energy deposited per pulse calculations for ZnS
Sr.No W α Sv tp pi
1 0,25 0,1 7,84E+12 5*10^(-9) 3,14159
Energy deposited per pulse
7,69E+02
Energy deposited per pulse
51
Mass evaporated of ZnS per pulse is demonstrated in Table 5.1.4.
Table 5.1.4: Mass vaporized per pulse for ZnS
Sr.No
Density
(kg/m3) pi w
Thermal
diffusivit
y, D,m2/s tp
1 4090 3,14159 0,25 4,14E-05 5*10^(-9)
Mass vaporized per pulse
3,65E-04
Mass vaporized per pulse
Table 5.1.5 demonstrates the results of mass evaporated and transformed in 1 hr by laser
operation.
Table 5.1.5: Mass evaporated and transformed per hour for laser operation
Sr.No
Density
(kg/m3) w
Thermal
diffusivit
y, D,m2/s Np tp
Mass evapoarted
and transformed in
1hr by laser
operation
1 4090 0,25 4,14E-05 30 5*10^-9 1,20E-01
Mass evaporated and
transformed in 1 min
by laser operation
2,00E-03
Mass evaporated and transformed/hr of laser operation
Figure 5.1 demonstrates the graph drawn between the material and its mass evaporated and
transformed per kg in an hour.
Figure 5.1: Mass Evaporated and transformed for ZnS
0,00E+00
1,00E-01
2,00E-01
ZnS
1,20E-01
kg/hr
Mass evaporated and transformed
52
5.2. Gases
Table 5.2.1 demonstrates the data, required in order to find mass evaporated and transformed for
gases.
Table 5.2.1: Data table for nitrogen oxides
Sr.No Toxic Gases
Density
(kg/m3)
Vaporization
temperature
Tv,K
Thermal
diffusivity,
D,m2/s
Heat of
fusion,Lm,
J/kg
Heat
Capacity,C,J
/kgK
1 NO 1270 121 1,99E-08 76667 Cp= 966
2 NO2 2620 294 1,99E-08 142174 Cp= 781
Thermal diffusivity values demonstrated in Table 5.2.1 are of oxygen.
Power density calculations for gases are demonstrated in Table 5.2.2.
Table 5.2.2: Power Density calculations for nitrogen oxides
Sr.No Toxic Gases
Density
(kg/m3)
Vaporizat
ion
temperat
ure Tv,K
Thermal
diffusivit
y, D,m2/s
Heat of
fusion,L
m, J/kg
Heat
Capacity,
C,J/kgK Power Density
1 NO 1270 121 1,99E-08 76667 966 -253540455,2
2 NO2 2620 294 1,99E-08 142174 781 7308496267
Power Density
Table 5.2.3: Energy deposited per pulse calculations for nitrogen oxides
Sr.No w α Sv tp pi
1 0,25 0,1 2,54E+08 5*10^(-9) 3,14159
2 0,25 0,1 7,31E+09 5*10^(-9) 3,14159
Energy deposited per pulse
Energy deposited per pulse
2,49E-02
7,17E-01
Mass evaporated of gases per pulse is demonstrated in Table 5.2.4.
Table 5.2.4: Mass vaporized per pulse calculations for nitrogen oxides
Sr.No
Density
(kg/m3) pi w
Thermal
diffusivit
y, D,m2/s tp
1 1270 3,14159 0,25 1,99E-08 5*10^(-9)
2 2620 3,14159 0,25 1,99E-08 5*10^(-9)
Mass vaporized per pulse
Mass vaporized per pulse
2,49E-06
5,13E-06
53
Table 5.2.5 demonstrates the results of mass evaporated and transformed in 1 hr by laser
operation.
Table 5.2.5: Mass evaporated and transformed per hour of laser operations for nitrogen oxides
Sr.No
Density
(kg/m3) w
Thermal
diffusivit
y, D,m2/s Np tp
Mass evaporated
and transformed
in 1 hr
1 1270 0,25 1,99E-08 30 5*10^-9 8,17E-04
2 2620 0,25 1,99E-08 30 5*10^-9 1,69E-032,81E-05
Mass evaporated and
transformed in 1 min
by laser operation
1,36E-05
Mass evaporated and transformed/hr of laser operation
Figure 5.2 demonstrates the graph drawn between the gases and their mass evaporated and
transformed per kg in an hour.
0
0,0005
0,001
0,0015
0,002
NONO2
0,000817441
0,001686375
kg/hr
Mass evaporated and transformed
Figure 5.2: Mass Evaporated and transformed for Nitrogen mono-oxide and Nitrogen dioxide
5.3. Liquids
Table 5.3.1 demonstrates the data, required in order to find mass evaporated and transformed for
liquids.
54
Table 5.3.1: Data table for acids, bases and organic solvents
Sr.No Toxic Liquids
Density
(kg/m3)
Vaporizat
ion
temperat
ure Tv,K
Thermal
diffusivit
y, D,m2/s
Heat of
fusion,L
m, J/kg
Heat
Capacity,
C,J/kgK
1 Hydrogen Iodide (HI) 2850 238 2,12E-07 22437 228,3
2 Formic Acid (HCOOH) 1220 374 1,99E-08 275472 2200
3 Nitric Acid (HNO3) 1510 356 1,99E-08 166640 1740
4 Hydrogen peroxide (H2O2) 1450 423 1,99E-08 367488 1267
5 Acetic Acid (CH3COOH) 1050 392 1,99E-08 195330 2043
6 Boric Acid (H3BO3) 1440 573 1,99E-08 360666 1392
7 Sulfuric Acid (H2SO4) 1840 610 1,99E-08 109197 1340
8 Benzoic Acid (C6H5COOH) 1270 522 8,70E-05 147559 1238
9 Hydrogen Bromide (HBr) 1490 206 4,16E-08 29786 351
10 Hydrochloric Acid (HCl) 1490 188 5,95E-09 54853 798
11 Sodium bicarbonate (NaHCO3) 2200 1124 1,99E-08 297594 1043
12 Sodium bicarbonate (NaHCO3) 2200 1124 1,99E-08 297594 1043
13 Sodium carbonate (Na2CO3) 2540 1906 1,19E-04 280188 1060
14 Ammonia (NH3) 682 240 9,90E-09 332335 2061
15 Potassium Hydroxide (KOH) 2044 1600 1,99E-08 140806 1228
17 Lithium Hydroxide, LiOH 1460 1197 1,99E-08 872651 2071
18 Sodium Hydroxide, NaOH 2130 1661 1,19E-04 165000 1488
19 Calcium Oxide, CaO 3350 3123 1,99E-04 1426599 749
20 Acetic Acid, CH3COOH 1050 391 1,99E-08 195330 2053
21 Methanol, CH3OH 792 338 1,99E-08 100343 2531
22 Propanol, CH3CH2CH2OH 803 370 8,70E-05 89357 2395
23 Ethanol CH3CH2OH 789 352 8,70E-05 107036 2438
24 Isopropanol, (CH3)2CHOH 786 356 8,70E-05 90016 2604
25 Methylene Chloride, CH2Cl2 1330 313 5,95E-09 54162 1192
26 n-heptane, C7H16 684 371 8,70E-05 140005 2242
27 Toulene, C7H8 867 384 8,70E-05 72064 1707
28 Propylene carbonate, C4H6O3 1205 513 1,99E-08 78362 2141
29 Benzene, C6H6 876 353 8,70E-05 126360 1055
30 Acetone, (CH3)2CO 791 330 8,70E-05 99345 2175
31 methly tert-butyl ether, C5H12O 740 328 8,70E-05 86216 2127
32 Formic Acid, HCOOH 1220 374 1,99E-08 275472 2151
33 Chloroform, CHCl3 1483 334 5,95E-09 79577 956
34 tetrachloro-ethylene, C2Cl4 1620 394 5,95E-09 65609 864
As mentioned earlier there were few values whose data were not available so those values are
used for a material which has high molar mass. It is demonstrated in Table 5.3.2.
55
Table 5.3.2: Variations used in data search. As the data for all the materials was not available
Sr.No Toxic Liquids
1 Hydrogen Iodide (HI)
2 Formic Acid (HCOOH)
3 Nitric Acid (HNO3)
4 Hydrogen peroxide (H2O2)
5 Acetic Acid (CH3COOH)
6 Boric Acid (H3BO3)
7 Sulfuric Acid (H2SO4)
8 Benzoic Acid (C6H5COOH)
9 Hydrogen Bromide (HBr)
10 Hydrochloric Acid (HCl)
11 Sodium bicarbonate (NaHCO3)
12 Sodium bicarbonate (NaHCO3)
13 Sodium carbonate (Na2CO3)
14 Ammonia (NH3)
16 Sodium Hydride NaH
17 Lithium Hydroxide, LiOH
18 Sodium Hydroxide, NaOH
19 Calcium Oxide, CaO
20 Acetic Acid, CH3COOH
21 Methanol, CH3OH
22 Propanol, CH3CH2CH2OH
23 Ethanol CH3CH2OH
24 Isopropanol, (CH3)2CHOH
25 Methylene Chloride, CH2Cl2
26 n-heptane, C7H16
27 Toulene, C7H8
28 Propylene carbonate, C4H6O3
29 Benzene, C6H6
30 Acetone, (CH3)2CO
31 methly tert-butyl ether, C5H12O
32 Formic Acid, HCOOH
33 Chloroform, CHCl3
34 tetrachloro-ethylene, C2Cl4
Cp is of gas phase, thermal diffusivity of iodine
Cp at 20-100C, thermal diffusivity of oxygen
Thermal diffusivity of oxygen
Cp of gas, thermal diffusivity of oxygen
Thermal diffusivity of oxygen
Thermal diffusivity of oxygen
Thermal diffusivity of oxygen
Thermal diffusivity of graphite
Thermal diffusivity of bromine
Thermal diffusivity of chlorine
Thermal diffusivity of oxygen
Thermal diffusvity of Sodium
Thermal diffusivity of Calcium
Thermal diffusivity of oxygen
Thermal diffusivity of oxygen
Thermal diffusivity of oxygen
Thermal diffusivity of Sodium
Thermal diffusivity of Nitrogen
Thermal diffusivity of graphite
Thermal diffusivity of oxygen
Thermal diffusivity of chlorine
Thermal diffusivity of chlorine
Variables
Thermal diffusivity of graphite
Thermal diffusivity of graphite
Thermal diffusivity of oxygen
Cp of gas, thermal diffusivity of graphite
Thermal diffusivity of graphite
Thermal diffusivity of oxygen
Thermal diffusivity of graphite
Thermal diffusivity of graphite
Thermal diffusivity of graphite
Thermal diffusivity of chlorine
Thermal diffusivity of Sodium
56
Power density calculations for liquids are demonstrated in Table 5.3.3.
Table 5.3.3: Power density calculations for acids, bases and organic solvents
Sr.No Toxic Liquids
Densi
ty
(kg/m
3)
Vaporizat
ion
temperat
ure Tv,K
Thermal
diffusivit
y, D,m2/s
Heat of
fusion,L
m, J/kg
Heat
Capacity,
C,J/kgK
Power
Density
1 Hydrogen Iodide (HI) 2850 238 2,12E-07 22437 228,3 3760419934
2 Formic Acid (HCOOH) 1220 374 1,99E-08 275472 2200 8690851951
3 Nitric Acid (HNO3) 1510 356 1,99E-08 166640 1740 6491274914
4 Hydrogen peroxide (H2O2) 1450 423 1,99E-08 367488 1267 1,289E+10
5 Acetic Acid (CH3COOH) 1050 392 1,99E-08 195330 2043 6065200324
6 Boric Acid (H3BO3) 1440 573 1,99E-08 360666 1392 1,5833E+10
7 Sulfuric Acid (H2SO4) 1840 610 1,99E-08 109197 1340 1,1652E+10
8 Benzoic Acid (C6H5COOH) 1270 522 8,70E-05 147559 1238 2,5069E+11
9 Hydrogen Bromide (HBr) 1490 206 4,16E-08 29786 351 787921604
10 Hydrochloric Acid (HCl) 1490 188 5,95E-09 54853 798 -440122777
11 Sodium bicarbonate (NaHCO3) 2200 1124 1,99E-08 297594 1043 3,1969E+10
12 Sodium bicarbonate (NaHCO3) 2200 1124 1,99E-08 297594 1043 3,1969E+10
13 Sodium carbonate (Na2CO3) 2540 1906 1,19E-04 280188 1060 1,1412E+12
14 Ammonia (NH3) 682 240 9,90E-09 332335 2061 2345921752
15 Potassium Hydroxide (KOH) 2044 1600 1,99E-08 140806 1228 3,8372E+10
16 Sodium Hydride NaH 1400 1073 1,19E-04 1517 1,6417E+10
17 Lithium Hydroxide, LiOH 1460 1197 1,99E-08 872651 2071 5,254E+10
18 Sodium Hydroxide, NaOH 2130 1661 1,19E-04 165000 1488 5,8533E+11
19 Calcium Oxide, CaO 3350 3123 1,99E-04 1426599 749 9,6051E+12
20 Acetic Acid, CH3COOH 1050 391 1,99E-08 195330 2053 6053303824
21 Methanol, CH3OH 792 338 1,99E-08 100343 2531 2347184318
22 Propanol, CH3CH2CH2OH 803 370 8,70E-05 89357 2395 9,5996E+10
23 Ethanol CH3CH2OH 789 352 8,70E-05 107036 2438 1,124E+11
24 Isopropanol, (CH3)2CHOH 786 356 8,70E-05 90016 2604 9,4475E+10
25 Methylene Chloride, CH2Cl2 1330 313 5,95E-09 54162 1192 991910895
26 n-heptane, C7H16 684 371 8,70E-05 140005 2242 1,2741E+11
27 Toulene, C7H8 867 384 8,70E-05 72064 1707 8,3659E+10
28 Propylene carbonate, C4H6O3 1205 513 1,99E-08 78362 2141 7378994623
29 Benzene, C6H6 876 353 8,70E-05 126360 1055 1,465E+11
30 Acetone, (CH3)2CO 791 330 8,70E-05 99345 2175 1,0417E+11
31 methly tert-butyl ether, C5H12O 740 328 8,70E-05 86216 2127 8,4598E+10
32 Formic Acid, HCOOH 1220 374 1,99E-08 275472 2151 8646614751
33 Chloroform, CHCl3 1483 334 5,95E-09 79577 956 1769400792
34 tetrachloro-ethylene, C2Cl4 1620 394 5,95E-09 65609 864 2475148903
57
Energy deposited per pulse is demonstrated in Table 5.3.4 using the result of power density.
Table 5.3.4: Energy deposited per pulse for acids, liquids and organic solvents
Sr.No Toxic liquids w α Sv tp pi
1 HI 0,25 0,1 3760419934 5*10^(-9) 3,14159
2 HCOOH 0,25 0,1 8690851951 5*10^(-9) 3,14159
3 HNO3 0,25 0,1 6491274914 5*10^(-9) 3,14159
4 H2O2 0,25 0,1 12890170233 5*10^(-9) 3,14159
5 CH3COOH 0,25 0,1 6065200324 5*10^(-9) 3,14159
6 H3BO3 0,25 0,1 15833410707 5*10^(-9) 3,14159
7 H2SO4 0,25 0,1 11651750887 5*10^(-9) 3,14159
8 C6H5COOH 0,25 0,1 2,50688E+11 5*10^(-9) 3,14159
9 HBr 0,25 0,1 787921603,8 5*10^(-9) 3,14159
10 HCl 0,25 0,1 -440122777 5*10^(-9) 3,14159
11 NaHCO3 0,25 0,1 31968863638 5*10^(-9) 3,14159
12 NaHCO3 0,25 0,1 31968863638 5*10^(-9) 3,14159
13 Na2CO3 0,25 0,1 1,14116E+12 5*10^(-9) 3,14159
14 NH3 0,25 0,1 2345921752 5*10^(-9) 3,14159
15 KOH 0,25 0,1 38372156874 5*10^(-9) 3,14159
16 NaH 0,25 0,1 16416974000 5*10^(-9) 3,14159
17 LiOH 0,25 0,1 52539856048 5*10^(-9) 3,14159
18 NaOH 0,25 0,1 5,85327E+11 5*10^(-9) 3,14159
19 CaO 0,25 0,1 9,60512E+12 5*10^(-9) 3,14159
20 CH3COOH 0,25 0,1 6053303824 5*10^(-9) 3,14159
21 CH3OH 0,25 0,1 2347184318 5*10^(-9) 3,14159
22 CH3CH2CH2OH 0,25 0,1 95995822132 5*10^(-9) 3,14159
23 CH3CH2OH 0,25 0,1 1,12399E+11 5*10^(-9) 3,14159
24 (CH3)2CHOH 0,25 0,1 94475234272 5*10^(-9) 3,14159
25 CH2Cl2 0,25 0,1 991910895,2 5*10^(-9) 3,14159
26 C7H16 0,25 0,1 1,27409E+11 5*10^(-9) 3,14159
27 C7H8 0,25 0,1 83659279013 5*10^(-9) 3,14159
28 C4H6O3 0,25 0,1 7378994623 5*10^(-9) 3,14159
29 C6H6 0,25 0,1 1,46502E+11 5*10^(-9) 3,14159
30 (CH3)2CO 0,25 0,1 1,04173E+11 5*10^(-9) 3,14159
31 C5H12O 0,25 0,1 84598483359 5*10^(-9) 3,14159
32 HCOOH 0,25 0,1 8646614751 5*10^(-9) 3,14159
33 CHCl3 0,25 0,1 1769400792 5*10^(-9) 3,14159
34 C2Cl4 0,25 0,1 2475148903 5*10^(-9) 3,14159
Energy deposited per pulseEnergy
deposited per
pulse
3,69E-01
2,43E-01
8,53E-01
6,37E-01
1,27E+00
5,95E-01
1,55E+00
1,14E+00
5,75E+01
9,43E+02
5,94E-01
2,30E-01
9,42E+00
3,14E+00
1,12E+02
2,30E-01
3,77E+00
1,61E+00
5,16E+00
1,02E+01
8,31E+00
2,46E+01
7,74E-02
-4,32E-02
3,14E+00
8,49E-01
1,74E-01
9,28E+00
9,74E-02
1,25E+01
8,21E+00
7,24E-01
1,44E+01
1,10E+01
58
Mass evaporated of liquids per pulse is demonstrated in Table 5.3.5.
Table 5.3.5: Mass vaporized per pulse for acids, bases and organic solvents
Sr.No Toxic liquids
Densit
y
(kg/m3
) pi w
Thermal
diffusivit
y, D,m2/s tp
1 HI 2850 3,14159 0,25 2,12E-07 5*10^(-9)
2 HCOOH 1220 3,14159 0,25 1,99E-08 5*10^(-9)
3 HNO3 1510 3,14159 0,25 1,99E-08 5*10^(-9)
4 H2O2 1450 3,14159 0,25 1,99E-08 5*10^(-9)
5 CH3COOH 1050 3,14159 0,25 1,99E-08 5*10^(-9)
6 H3BO3 1440 3,14159 0,25 1,99E-08 5*10^(-9)
7 H2SO4 1840 3,14159 0,25 1,99E-08 5*10^(-9)
8 C6H5COOH 1270 3,14159 0,25 8,70E-05 5*10^(-9)
9 HBr 1490 3,14159 0,25 4,16E-08 5*10^(-9)
10 HCl 1490 3,14159 0,25 5,95E-09 5*10^(-9)
11 NaHCO3 2200 3,14159 0,25 1,99E-08 5*10^(-9)
12 NaHCO3 2200 3,14159 0,25 1,99E-08 5*10^(-9)
13 Na2CO3 2540 3,14159 0,25 1,19E-04 5*10^(-9)
14 NH3 682 3,14159 0,25 9,90E-09 5*10^(-9)
15 KOH 2044 3,14159 0,25 1,99E-08 5*10^(-9)
16 NaH 1400 3,14159 0,25 1,19E-04 5*10^(-9)
17 LiOH 1460 3,14159 0,25 1,99E-08 5*10^(-9)
18 NaOH 2130 3,14159 0,25 1,19E-04 5*10^(-9)
19 CaO 3350 3,14159 0,25 1,99E-04 5*10^(-9)
20 CH3COOH 1050 3,14159 0,25 1,99E-08 5*10^(-9)
21 CH3OH 792 3,14159 0,25 1,99E-08 5*10^(-9)
22 CH3CH2CH2OH 803 3,14159 0,25 8,70E-05 5*10^(-9)
23 CH3CH2OH 789 3,14159 0,25 8,70E-05 5*10^(-9)
24 (CH3)2CHOH 786 3,14159 0,25 8,70E-05 5*10^(-9)
25 CH2Cl2 1330 3,14159 0,25 5,95E-09 5*10^(-9)
26 C7H16 684 3,14159 0,25 8,70E-05 5*10^(-9)
27 C7H8 867 3,14159 0,25 8,70E-05 5*10^(-9)
28 C4H6O3 1205 3,14159 0,25 1,99E-08 5*10^(-9)
29 C6H6 876 3,14159 0,25 8,70E-05 5*10^(-9)
30 (CH3)2CO 791 3,14159 0,25 8,70E-05 5*10^(-9)
31 C5H12O 740 3,14159 0,25 8,70E-05 5*10^(-9)
32 HCOOH 1220 3,14159 0,25 1,99E-08 5*10^(-9)
33 CHCl3 1483 3,14159 0,25 5,95E-09 5*10^(-9)
34 C2Cl4 1620 3,14159 0,25 5,95E-09 5*10^(-9)
Mass vaporized per pulse
Mass vaporized
per pulse
1,82E-05
1,73E-06
2,39E-06
2,96E-06
2,84E-06
2,06E-06
2,82E-06
3,60E-06
1,64E-04
4,22E-06
9,58E-05
2,39E-06
1,59E-06
1,04E-04
1,02E-04
1,02E-04
1,42E-06
8,86E-05
1,12E-04
1,60E-06
4,31E-06
4,31E-06
3,85E-04
9,42E-07
4,00E-06
2,36E-06
1,13E-04
1,02E-04
2,12E-04
2,86E-06
3,23E-04
6,56E-04
2,06E-06
1,55E-06
59
Table 5.3.6 demonstrates the results of mass evaporated and transformed in 1 hr by laser
operation.
Table 5.3.6: Mass evaporated and transformed per hour for acids, bases and organic solvents
Mass evaporated and transformed/hr of laser operation
Sr.No Toxic liquids
Densit
y
(kg/m3
) w
Thermal
diffusivit
y, D,m2/s Np tp
Mass
evaporated and
transformed in 1
hr
1 HI 2850 0,25 2,12E-07 30 5*10^-9 5,99E-03
2 HCOOH 1220 0,25 1,99E-08 30 5*10^-10 7,85E-04
3 HNO3 1510 0,25 1,99E-08 30 5*10^-11 9,72E-04
4 H2O2 1450 0,25 1,99E-08 30 5*10^-12 9,33E-04
5 CH3COOH 1050 0,25 1,99E-08 30 5*10^-13 6,76E-04
6 H3BO3 1440 0,25 1,99E-08 30 5*10^-14 9,27E-04
7 H2SO4 1840 0,25 1,99E-08 30 5*10^-15 1,18E-03
8 C6H5COOH 1270 0,25 8,70E-05 30 5*10^-16 5,40E-02
9 HBr 1490 0,25 4,16E-08 30 5*10^-17 1,39E-03
10 HCl 1490 0,25 5,95E-09 30 5*10^-18 5,24E-04
11 NaHCO3 2200 0,25 1,99E-08 30 5*10^-19 1,42E-03
12 NaHCO3 2200 0,25 1,99E-08 30 5*10^-20 1,42E-03
13 Na2CO3 2540 0,25 1,19E-04 30 5*10^-21 1,26E-01
14 NH3 682 0,25 9,90E-09 30 5*10^-22 3,10E-04
15 KOH 2044 0,25 1,99E-08 30 5*10^-23 1,32E-03
16 NaH 1400 0,25 1,19E-04 30 5*10^-24 6,97E-02
17 LiOH 1460 0,25 1,99E-08 30 5*10^-25 9,40E-04
18 NaOH 2130 0,25 1,19E-04 30 5*10^-26 1,06E-01
19 CaO 3350 0,25 1,99E-04 30 5*10^-27 2,16E-01
20 CH3COOH 1050 0,25 1,99E-08 30 5*10^-28 6,76E-04
21 CH3OH 792 0,25 1,99E-08 30 5*10^-29 5,10E-04
22 CH3CH2CH2OH 803 0,25 8,70E-05 30 5*10^-30 3,42E-02
23 CH3CH2OH 789 0,25 8,70E-05 30 5*10^-31 3,36E-02
24 (CH3)2CHOH 786 0,25 8,70E-05 30 5*10^-32 3,35E-02
25 CH2Cl2 1330 0,25 5,95E-09 30 5*10^-33 4,68E-04
26 C7H16 684 0,25 8,70E-05 30 5*10^-34 2,91E-02
27 C7H8 867 0,25 8,70E-05 30 5*10^-35 3,69E-02
28 C4H6O3 1205 0,25 1,99E-08 30 5*10^-36 7,76E-04
29 C6H6 876 0,25 8,70E-05 30 5*10^-37 3,73E-02
30 (CH3)2CO 791 0,25 8,70E-05 30 5*10^-38 3,37E-02
31 C5H12O 740 0,25 8,70E-05 30 5*10^-39 3,15E-02
32 HCOOH 1220 0,25 1,99E-08 30 5*10^-40 7,85E-04
33 CHCl3 1483 0,25 5,95E-09 30 5*10^-41 5,22E-04
34 C2Cl4 1620 0,25 5,95E-09 30 5*10^-42 5,70E-04
5,16E-06
2,19E-05
6,21E-04
5,61E-04
5,25E-04
1,13E-05
8,50E-06
5,70E-04
5,60E-04
5,58E-04
7,80E-06
1,31E-05
1,62E-05
1,56E-05
1,13E-05
1,54E-05
1,97E-05
9,01E-04
2,31E-05
Mass
evaporated and
transformed in 1
min by laser
9,98E-05
9,50E-06
8,74E-06
2,36E-05
2,36E-05
2,11E-03
1,16E-03
1,57E-05
1,77E-03
3,59E-03
1,31E-05
8,70E-06
4,85E-04
6,15E-04
1,29E-05
60
Figure 5.3.1 demonstrates the graph drawn between the different acids and their mass evaporated
and transformed per kg in an hour.
Figure 5.3.1: Mass evaporated and transformed for liquids
5,99E-03
7,85E-04 9,72E-04 9,33E-04
6,76E-04 9,27E-04 1,18E-03
5,40E-02
1,39E-03
5,24E-04
0,00E+00
1,00E-02
2,00E-02
3,00E-02
4,00E-02
5,00E-02
6,00E-02
kg/hr
Acids mass evaporated/transformed
61
Figure 5.3.2 demonstrates the graph drawn between the different bases and their mass evaporated
and transformed per kg in an hour.
Figure 5.3.2: Mass evaporated and transformed for Bases
1,42E-03
1,42E-03
1,26E-01
3,10E-04 1,32E-03
6,97E-02
9,40E-04
1,06E-01
2,16E-01
0,00E+00
5,00E-02
1,00E-01
1,50E-01
2,00E-01
2,50E-01
NaHCO3 NaHCO3 Na2CO3 NH3 KOH NaH LiOH NaOH CaO
kg/hr
Bases mass evaporated/transformed
62
Figure 5.3.3 demonstrates the graph drawn between different organic solvents and their mass
evaporated and transformed per kg in an hour.
Figure 5.3.3: Mass evaporated and transformed for Organic solvents
6,76E-04
5,10E-04
3,42E-02 3,36E-02 3,35E-02
4,68E-04
2,91E-02
3,69E-02
7,76E-04
3,73E-02
3,37E-02 3,15E-02
7,85E-04
5,22E-04
5,70E-04
0,00E+00
5,00E-03
1,00E-02
1,50E-02
2,00E-02
2,50E-02
3,00E-02
3,50E-02
4,00E-02
kg/hr
Organic solvents mass evaporated/transformed
63
6. Proposal of laser reactor for decomposition of toxic materials
Though the funding was not available for the project but the reactor was designed incase funds
become available and experiments can be carried out for all the toxic materials in order to
support the mathematical models. This project only contains the experiments of NOx.
With reference to the above figure, drawn in Solid Edge (3D modeling software); we can observe
that the stainless steel reactor is formed with a multilayer of materials that can diffuse and resist
the heat. The internal layer is made of a highly reflective and high temperature resistance
ceramic (Shuttle technology coated with hard super white ceramic). A layer of copper will fast
transmit the heat to the main frame. Figure 6.1 demonstrates the reactor drawn in solid edge.
Figure 6.1: Stainless steel reactor for the decomposition of toxic materials through laser made in Solid Edge
The dimensions are purely indicative. Final dimension values will be determined using finite
element analysis and suitable software (COMSOL) in order to have the best cooling efficiency
along with perfect sealing in order to avoid leakages of toxic materials. In this respect it is
64
obvious that the experimental set-up will be inside a special with all the safety measure to protect
the laboratory staff and external environment.
The drawings do not show the laser and the ancillary instruments but only the optical window
interfaces to all the devices. The experiment will use:
1- A series of lasers:
a- Low cost semiconductor laser with NIR, Green and UV lines, with low energy (12
µJ) but very short pulse with (0.1 ns) and high pulse repetition frequency (prf > 5
kHz)
b- Medium energy laser 2.5 J @ 1064 nm fundamental wavelength with outputs at 532
nm e 266 nm and very high energy > 100 J @106 nm
2. Spectrometers
3. Strike camera in the visible
4. Strike camera in the IR
5. Series of standard video camera
6. Thermal imagers (FLIR)
7. Gas analyzers
8. Oscilloscopes
9. Multi-meters
10. Flow controllers for liquids and gases
Beside software (COMSOL, Mathematica, etc.) and lap tops
Why spherical shape? First of all the sphere is the best black-body absorber and producer of
standing waves, thus enhancing the mechanism of optical breakdown of molecular bonds. The
inner spherical shape of the bottom parts allow its use for liquids and solids whereas gases can be
adiabatically expanded through one of the access in the horizontal plane and the laser beam
secured at the opposite of the adiabatic expansion nozzle. The single block with square shape in
which the bottom half sphere is realized enables absorbing and diffusing the excess of heat in the
65
reaction chamber. We could select a less complicated geometry adopting a cylindrical structure
for the reactor. But, this solution is less effective than the spherical geometry.
Figure 6.2 demonstrates the cross section that shows the internal layout of the reactor. In order to
contain the extremely hot plasma temperature and do not affect metals a multi-layer structure has
been conceived. Dimensions of layers are not defined and not in proportion. The ceramic is full
reflecting white absolving two functions:
1. Reflecting back to the center of the sphere the wavelength packets emitted by the plasma
activated by the laser
2. Shielding the heat and dumping the temperature transmission.
Figure 6.2: Cross-sectional view of stainless steel reactor made in AutoCAD
66
The external upper part of the reactor is made in stainless steel as demonstrated in Figure 6.3.
Figure 6.3
The external bottom part of the reactor also made in stainless steel. The external part of the
bottom is flat for easy positioning. It is demonstrated in figure 6.4.
Figure 6.4
67
The two half portion of the sphere in copper for fast cooling and transmission to the external
shield. They are demonstrated in figure 6.5 and figure 6.6.
Figure 6.5
Figure 6.6
68
The inner two half spheres made in ceramic. They are demonstrated in Figure 6.7 and Figure 6.8.
Figure 6.7
Figure 6.8
69
Figure 6.9
Particular of the sapphire windows supports. O-ring seals are not visible. These duct support are
deigned to ensure perfect sealing of the sphere, they will be tested with high pressure pumping
inside the sphere air at 10 ATM in order to ensure that no leaks may occur during operation for
safety reasons. AS already stated these are preliminary drawings and do not show details like
seals sits and lenses or optical windows seats. Windows are necessary in this experimental
reactor in order to ensure the access to optical devices like spectrometers, high speed strike
camera, IR camera, thermal vision units, and Schlieren camera.
70
7. Experimental decomposition of NOx
Lasers can be used to efficiently decompose NOx, and research in this direction may pay back
when efficient (optical/electrical power >60%) solar powered solid state lasers can be employed.
Laser beams can be easily and efficiently manipulated and controlled, maintaining the required
field values. Laser beams can be transformed into thin blades of light and very rapidly scan
matrices of nozzles.
A NOx environmental mixture of N2O, Nitrous oxide 397 ppmmol, NO (Nitrogen mono-oxide)
890 ppmmol and NO2 (Nitrogen Dioxide) 9 ppmmol were flown into an insulate reactor. The
reactor has two sections which were separated by a diaphragm of 1mm diameter. The flow of
NOx could be controlled by mass flow controller. In the second section, the diaphragm enables
NOx adiabatic expansion under the action of a high pulse energy laser beam focused on the 1mm
aperture. The decomposed gas flows into the spectrometer when the depression pump is active;
this reduces the gas in second section of reactor.
A sapphire window ensures that all the gases will flow into the spectrometer. The polluted gas
flow is actively controlled with a commercially available feedback system. A laser beam is fed
through a protective pipe into the reactor, and its minimum beam waist was perfectly aligned on
the circular aperture of the diaphragm. Pre-alignment of the system was done using a 5 MW, 532
nm green laser beam. The minimum beam waist must not touch the diaphragm walls since the
laser beam will increase their temperature and consequently, NOx population will increase.
Actually, this misalignment was utilized as trivial test to check if really NOx were decomposed
by the laser heating up the diaphragm body.
The laser used was Q-switched Nd:YAG with fundamental wavelength of 1064 nm with pulse
trains having a fixed duration of 8ns each. The lamp repetition frequency ranging from 1 Hz to
20 Hz with energy variation from 0 J to 1.6 J.
Energy setting is quite accurate as the lamp current is preset through a 3 digits code having the
threshold at the digit code 135 and the maximum at the digit code 210. The diagram of figure 5
shows the correspondence between the 3 code system (in the figure reported as “bit” for sake of
simplicity) and the energy output outside the focusing lens. Values were previously factory
71
measured with the high quality Thermopile Analog Laser Power Meter PMW1 calibrated on the
Ophir-Spiricon energy meter.
NOx flow set was 450 ml. The values of the flow range combined with the spectrometer
depression enables NOx not to dissipate outside the reactor due to leaks in the reactor’s joints.
Laser interaction time was 10’. At 10’ the laser was put off and the NOx concentration in ppm
was measured reaching the starting value in almost 2’ time. The delay was due to the pipe length
between the reactor and the spectrometer.
Experimental setup is demonstrated in Figure 7.1, Figure 7.2, and Figure 7.3.
Figure 7.1: Layout of the experiment
72
Figure 7.2: NOx bottle, Reactor, Mass Flow Controller and spectrometer
Figure 7.3: Reactor where adiabatic expansion occurs NOx decomposition
73
8. Results and Discussion
In order to understand behavior of materials when exposed to lasers two mathematical models
are made and experiments are carried out on NOx. As NOx is the only material on which
experiments were carried out so the results of the experiments are given below and later they are
compared with the mathematical model results of NOx.
8.1. Experimental The results obtained from the experiments are shown in the following curves. The following
curves are drawn between parts per million of NOx against time the NOx is exposed to the laser.
They have two curves because the tests were repeated twice in order to have reliability of the
readings. The laser energy demonstrated in curves of Figure 8.1, Figure 8.2, Figure 8.3, and
Figure 8.4 have been increased and with that the ppm of NOx decreases. The curves show NOx
concentration in the adiabatic expansions room versus laser beam-on time at 20 Hz for a total
exposure time of 96 µs in 10’ time interval at increasing laser energy: 0.532 J, 0.64 J, and 0.961
J.
Figure 8.1: ppm v/s time for 0.532 J
0 2 4 6 8 10 12550
600
650
700
750
800
850
t '
ppm
NOx vs Time 0.532J & 20.0Hz
74
Figure 8.2: ppm v/s time for 0.64 J
Figure 8.3: ppm v/s time for 0.96 J
0 2 4 6 8 10 12
500
600
700
800
t '
ppm
NOx vs Time 0.64J & 20.0Hz
0 2 4 6 8 10 12
300
400
500
600
700
800
t '
ppm
NOx vs Time 0.96J & 20.0Hz
75
When the test was being conducted at 1.17 J the sapphire window broke and the readings were
not taken twice. The sapphire window was broken due to excess heat deposited at 1.17 J per
pulse. Despite the broken window the gas flow was basically contained inside the reactor volume
and still consistent NOx decomposition was observed.
Figure 8.4: The NOx concentration in the adiabatic room at sapphire break (a 2.2 mm hole)
The results obtained from the experiments show that the concentration of NOx decreases when
it’s exposed to lasers. Secondly, the experiments have shown that with the increase in energy the
concentration of NOx decreases, which means with the increase in energy the toxic material
destruction increases as well. Experiments show that with the increase of laser energy the
destruction of NOx increases.
8.2. Methematical models
Now we look at the results of two mathematical models and see their results. In case of
molecular dissociation model using laser of higher energy gives higher value for material
destroyed. It can be seen in the following comparative graphs for molecular dissociation model.
0 2 4 6 8 10 12
300
400
500
600
700
800
t '
ppm
NOx vs Time 1.17J & 20.0Hz
76
Figure 8.5: Destruction of NOx according to molecular dissociation model using 2.865J Laser
Figure 8.6: Destruction of NOx according to molecular dissociation model using 286.5J Laser
Destruction of NOx according to molecular dissociation model shown in the above two figures
reveal that with the increase of the energy of laser the amount of destruction of the material has
increased. The exact same relationship has been found in the experiment as well.
0,00E+00
5,00E-01
1,00E+00
1,50E+00
2,00E+00
NO NO2
9,43E-01
1,91E+00
m3/hr
Gases destruction by 2.865J Laser
0,00E+00
5,00E+01
1,00E+02
1,50E+02
2,00E+02
NO NO2
9,42E+01
1,91E+02
m3/hr
Gases destruction by 286.5J Laser
77
Plasma exploitation model shown in Figure 8.7 when compared with molecular dissociation
model shows the same trend for NO and NO2 destruction amount per hour. Higher is for NO2
and lower amount of NO. This is because the decomposition energy for NO is higher than that of
NO. But plasma exploitation model also ensure the destruction of NOx.
Figure 8.7: Destruction of NOx according to plasma exploitation model
From the above results of the same material it can be concluded that the mathematical models as
well as the experiments are in agreement about the destruction of NOx by lasers. Moreover,
experiment and molecular dissociation model show a directly proportional relationship between
the laser energy and amount of destruction. Graphical results of two mathematical models predict
that amount of destruction of NO2 is more than that of NO. It’s because of difference of
decomposition energies.
The same relationship for the increase of laser energy is observed in all the toxic materials that
have been studied. Following two graphs also show the increase of laser energy increases the
amount of destruction of toxic material.
0
0,0005
0,001
0,0015
0,002
NONO2
0,000817441
0,001686375
m3/hr
Mass evaporated and transformed/hr
78
Figure 8.8: Destruction of acids according to molecular dissociation model using 2.865J Laser
Figure 8.9: Destruction of acids according to molecular dissociation model using 2.865J laser
6,22E+00
6,76E-01
3,35E-01
8,64E-01 4,50E-01
4,25E-01
2,16E+01
2,67E+00
3,00E-01
8,99E-01
5,38E+00
9,43E-01
0,00E+00
5,00E+00
1,00E+01
1,50E+01
2,00E+01
2,50E+01
m3/hr
Acids destroyed by 2.86J Laser
6,22E+02
6,75E+01
3,35E+01
8,63E+01
4,50E+01
4,24E+01
2,15E+03
2,66E+02
3,00E+01 8,98E+01
5,38E+02
9,42E+01
0,00E+00
5,00E+02
1,00E+03
1,50E+03
2,00E+03
2,50E+03
m3/hr
Acids destroyed by 286.5J Laser
79
As the laser energy is increased by 100 times the amount of destruction of toxic material is also
increased by the same factor. Different materials have a difference response towards the same
energy of Laser. It is because of the material’s decomposition energy. H3BO3 having the highest
amount of destruction has lowest decomposition energy of 7195 J/mol. The lowest amount of
destruction is for C6H8O7 and it has the highest decomposition energy of 1384000 J/mol. This is
same with bases as well as organic solvents.
Plasma exploitation model for acids shown in following figure also show the destruction of acids
but the amount of destruction of acids is not proportional to the amount of destruction predicted
by molecular dissociation method.
Figure 8.10: Results for plasma exploitation model of acids
The difference between the values of the two models is because in molecular dissociation the
values are calculated for the decomposition of materials into elements but in plasma exploitation
model values are calculated for the decomposition of materials into plasma. This is the reason for
the change in values but both the models ensure the destruction of toxic and non-toxic waste.
5,99E-03
7,85E-04
9,72E-04
9,33E-04 6,76E-04
9,27E-04
1,18E-03
5,40E-02
1,39E-03
5,24E-04
0,00E+00
1,00E-02
2,00E-02
3,00E-02
4,00E-02
5,00E-02
6,00E-02
m3/hr
Acids mass evaporated/transformed per hr
80
In case of laser molecular dissociation we found that the dissociation energies involved demand
very high energy lasers. The only laser which can be utilized delivering in rapid sequence
packets of photons equivalent to the total amount required is the Gas Dynamic pulsed CO2 laser
developed by Prof. Viktor Apollonov, with 100 kW peak power and 5ns pulse width (2.86 J)
with a typical pulse repetition frequency of 350 kHz at a 10640.0 nm wavelength. Delivery of
photons must be faster than relaxation times of molecule contribute to further decompose the
toxic material. This part was not developed further owing to the problems of patenting this
technology. A U.S. patent, presently expired, was already issued in past but laser source and
applications were not complete.
As already stated, both the methods lead to theoretical confirmation that there are available laser
sources capable to destroy toxic materials at reasonable rates but with greater efficiencies with
respect to prevailing conventional methods, whose maximum efficiency reach 98%. A third
process, photolysis could not be thoroughly evaluated. But, our experimental results on NOx
confirm that also photolysis can be utilized especially in case of gases and vapors.
8.3. Conclusions from results and discussion
In conclusion lasers do effectively demolish toxic materials in a selective and most efficient way.
Not only, the three methods - being complimentary - may be combined in a way to ensure total,
100%, total destruction of extremely dangerous toxic waste, like those produced in hospitals
containing also contaminants.
In case of laser plasma interaction the laser splits molecules in ions and electrons confining this
plasma within the same beam. The interactions increase the plasma temperature until laser
sustained combustion appears. But, the laser interaction with the plasma produces a very wide
band of secondary photons, which enhanced and confined in a black-body spherical cavity
81
9. Acknowledgments
I would like to express my great thanks to Dr. .Muhammad Muddassir Silvio Gualini for his
dedication and commitment for the completion of this project even after great hurdles. His
constant supervision, great motivation and extreme interest lead me to the completion of this
project. Dr. Anders Eliasson and Dr. Hasse Fredriksson have played a key role in the completion
of my degree and I thank them for allowing me to work on this project. I would also like to thank
R. Angelo Ferrario, Quanta system and GAP Laser & Photonics management for supplying
lasers and ancillary equipment. Finally I thank my parents from whom I always got great comfort
for the completion of this project.
82
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Appendix
1. Solids
1.1. Phosphors
Table 1: Conventional technology to destroy Scheelite and Scheelite Wolframite concentrates
SCHEELITE AND SCHEELITE-WOLFRAMITE CONCENTRATES Items to compare
Conventional technology
Destruction technology
Caustic decomposition through mechanical activation
Efficiency 98%
Amount of destruction
By Products No
Skilled Labor Yes
Dangerous process
No
Automatic Yes
PTOTMBD No
Investment cost High
Running cost High but it is used in 11 plants in China
Working Area Very Large
Number of Labor More than 1
Comments Short life of equipment for the friction between steel ball and cylinder “Caustic decomposition of scheelite and scheelite-wolframite concentrates through mechanical activation”, Li Honggui, Liu
Maosheng, Sun Peimei, Li Yunjiao, J.CENT. South Univ. Technol. Vol.2 No.2, [15]
Table 2: Conventional technology to destroy Scheelite and Scheelite Wolframite mixed concentrates
SCHEELITE AND SCHEELITE-WOLFRAMITE MIXED CONCENTRATES
Items to compare
Conventional technology
Destruction technology
caustic soda digestion
Efficiency 98%
Amount of destruction
By Products No
Skilled Labor No
Dangerous No but it can become if the pressure in the autoclave exceeds safe
104
process value
Automatic Yes
PTOTMBD No
Investment cost Low as just an autoclave required
Running cost Small as just an autoclave is required and the raw materials with few additives
Working Area Small
Number of Labor 1
Comments ”Decomposition scheelite and scheelite-wolframite mixed concentrated by caustic soda digestion”, Sun Pei-mei, Li Hong-gui, LI
Yun-Jiao, ZHAO Zhong-wei, HUO Guang-sheng, SUN Zhao-ming, LUI Mao-Sheng, J.CENT. South. Univ. Technol. Vol.20, No4, [16]
Table 3: Conventional technology to destroy KH2PO4 Crystals
KH2PO4 CRYSTALS
Items to compare
Conventional technology
Destruction technology
Laser induced decomposition
Efficiency 98%
Amount of destruction
Yes as lasers and examination tools are sophisticated
By Products No
Skilled Labor No
Dangerous process
Yes
Automatic High because of Raman Scattering, photoluminescence and soft X-ray absorption near edge structure spectrometers are required
PTOTMBD Low
Investment cost 1
Running cost Laser induced material decomposition at surface damage sites but not at bulk damage sites
Working Area
Number of Labor
Comments ”Decomposition of KH2OP4 crystals during laser-induced breakdown”, R.A. Negres, S.O. Kucheyev, P. DeMange, C.Bostedt, T.van
Buuren, A.J. Nelson, S.G. Demos, Applied Physics Letters 86, 171107, [17]
Table 4: Conventional technology to destroy Scheelite
SCHEELITE
Items to compare
Conventional technology
Destruction technology
Acid-alcohol solution i.e. HCl and absolute ethanol
Efficiency 100%
105
Amount of destruction
Tungstic Acid
By Products No
Skilled Labor No
Dangerous process
No
Automatic No
PTOTMBD Low
Investment cost Low
Running cost Small
Working Area 1
Number of Labor
Comments ”Decomposition of scheelite in acid-alcohol solutions”, S.Ozdemir, I. Girgin, Minerals Engineering Vol.4 No.2, pp.179-184, 1991,
[18]
Table 5: Conventional technology to destroy LiGDF4 Scheelite
LIGDF4 SCHEELITE
Items to compare
Conventional technology
Destruction technology
high pressure (11GPa) and temperature
Efficiency LiF
Amount of destruction
Yes
By Products No
Skilled Labor Yes
Dangerous process
No
Automatic High as we need X-rays
PTOTMBD Low
Investment cost
Running cost 1
Working Area
Number of Labor
Comments ”Decomposition of LiGdF4 scheelite at high pressures”, Andrzej Grzechnik, Wilson A Crichton, Pierre Bouvier, Vladimir Dmitriev,
Han’Peter Weber, Jean Yves Gesland, Journal of Physics: Condensed Matter, [19]
Table 6: Conventional technology to destroy Zinc Sulphide
ZINC SULPHIE
Items to compare
Conventional technology
Destruction Decomposition by the reaction of atomic hydrogen with ZnS
106
technology
Efficiency
Amount of destruction
By Products No
Skilled Labor
Dangerous process
Automatic
PTOTMBD No
Investment cost
Running cost
Working Area
Number of Labor
Comments ”Electron-hole mechanism for the decomposition of zinc sulfide in a hydrogen atmosphere”, V.F. Kharlamov, V.V. Styrov, A.P.
Il’in and I.Z. Gorfunkel, Russian Physics Journal Volume 19, Number 10, 1273-1277, [20]
Table 7: Conventional technology to destroy Sodium Tungsten
SODIUM TUNGSTEN
Items to compare
Conventional technology
Destruction technology
Decomposition using melt of NaCl-NaF-NaCO3 salt system and using Al
Efficiency 90%
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process
Automatic No
PTOTMBD No
Investment cost High as X-Ray diffractometer is required
Running cost High as the mixture is kept over 1000 °C for 1 hour
Working Area
Number of Labor
Comments ”Obtaining tungsten powder from the scheelite concentration in Ion Melts”, V.V. Gostishchev and V.F. Boiko, Theoretical
Foundations of Chemical Engineering 2008, Vol.42, No.5, pp. 728-730, [21]
Table 8: Conventional technology to destroy Co2, Ni2, Cu2, Zn2, Cd2 and Pb2 m-benzenedisulphates in air and in nitrogen atmospheres
Co2,Ni2,Cu2,Zn2,Cd2 and Pb2 m-benzenedisulphates in air and in nitrogen atmospheres
107
Items to compare
Conventional technology
Destruction technology
Thermal decomposition in air and in nitrogen atmospheres
Efficiency
Amount of destruction
By Products
Skilled Labor Yes to operate DTA, DSC and X-ray diffractometer
Dangerous process
No
Automatic No
PTOTMBD Yes
Investment cost High due to DTA,DSC and TG, X-ray diffractometer
Running cost Low
Working Area Large as X-ray diffractometer, DTA, DSC and TG are required
Number of Labor 1
Comments ”Synthesis and thermal decomposition of Co2, Ni2, Cu2, Zn2, Cd2 and Pb2 m-benzenedisulphates” Araceli Ramirez Garcia,
Alejandro Guerrero Laverat, C. Victoria Ragel Prudencio and Antonio Jerze Mendez, Thermochimica Acta, 213(1993) 199-210,
[22]
Table 9: Conventional technology to destroy Co2, Ni2, Cu2, Zn2, Cd2, and Pb2 hydroxy-p-toluenesulphonates
Co2,Ni2,Cu2,Zn2,Cd2 and Pb2 hydroxy-p-toluenesulphonates
Items to compare
Conventional technology
Destruction technology
Thermal decomposition in air and in nitrogen atmospheres
Efficiency
Amount of destruction
By Products Different products for air and nitrogen atmospheres
Skilled Labor Yes for diffractometer, spectrophotometer, DTA, TG
Dangerous process
No
Automatic No
PTOTMBD Yes
Investment cost High due to DTA, TG, X-ray diffractometer, spectrophotometer
Running cost Low
Working Area Large as spectrophotometer, TG,DSC and diffractometer are required
Number of Labor 1
Comments ”Thermal decomposition of Co2, Ni2, Cu2, Zn2, Cd2 and Pb2 hydroxy-p-toluenesulphonates”, Mercedes Bombin, MA Martinez-
Zaporta, Araceli Ramirez, Alejandro Geurero and Antonio Jerez Mendez, Thermochimica Acta, 224 (1993) 151-163, [23]
108
Table 10: Conventional technology to destroy artificial scheelite
ARTIFICAL SCHEELITE
Items to compare
Conventional technology
Destruction technology
Mechanism of artificial scheelite decomposition in Nitric Acid
Efficiency
Amount of destruction
By Products
Skilled Labor
Dangerous process
Automatic
PTOTMBD
Investment cost
Running cost
Working Area
Number of Labor
Comments The spaces are left as the paper discusses only the mechanism ”Investigation of the Mechanism of Decomposition of artificial Scheelite in Nitric Acid”, Eshmurat A. Pirmatov, Chemistry for
sustainable development 11 (2003) 635-637, [24]
1.2. Asbestos
Table 11: Conventional technology to destroy Friable Asbestos
FRIABLE ASBESTOS
Items to compare
Conventional technology
Destruction technology
Decomposition using acidic gas (HF and HCl) generated by the decomposition of CHClF2 with superheated steam
Efficiency 100%
Amount of destruction
10 g / 30 mins
By Products Just exhaust gas
Skilled Labor Yes
Dangerous process
No
Automatic Yes
PTOTMBD No
Investment cost High because of X-ray diffractometer and SEM
Running cost
Working Area
109
Number of Labor 1
Comments ” A novel decomposition technique of friable asbestos by CHClF2-decomposed acidic gas”, Kazumichi Yanagisawa, Journal of
Hazardous Materials, [25]
Table 12: Conventional technology to destroy Asbestos
ASBESTOS
Items to compare
Conventional technology
Destruction technology
Decomposition through Sulfuric acid
Efficiency
Amount of destruction
By Products Silica
Skilled Labor
Dangerous process
No. There is high degree of safety
Automatic
PTOTMBD
Investment cost
Running cost Low running cost because of the cheap chemical compounds
Working Area
Number of Labor
Comments By-products are solidified ”Asbestos Decomposition”, Song-Tien Chou, Manhattan, Kans, ASD, Inc. Houston, Tex, [26]
Table 13: Conventional technology to destroy Chrysotile Asbestos
CHRYSOTILE ASBESTOS
Items to compare
Conventional technology
Destruction technology
Decomposition by Fluorosulfonic Acid
Efficiency
Amount of destruction
By Products SiO2
Skilled Labor Yes for XRD,SEM, Spectrometer but not for experiments
Dangerous process
No
Automatic Yes
PTOTMBD No
Investment cost High because of FT-IR, Spectrometer, XRD and SEM
110
Running cost Low as only chemical reagents are required
Working Area Very small except for the examination machines
Number of Labor 1
Comments ”Decomposition of Chrysotile Asbestos by Fluorosulfonic Acid”, T.Sugama, R.Sabatini, L.Petrakis, Ind.Eng.Chem.Res. 1998, 37,
79-88, [27]
Table 14: Conventional technology to destroy Asbestos Fibers
ASBESTOS FIBERS
Items to compare
Conventional technology
Destruction technology
Low temperature sintering
Efficiency
Amount of destruction
By Products No
Skilled Labor Yes
Dangerous process
No
Automatic No
PTOTMBD Yes
Investment cost High
Running cost High because furnace is operated over 1000 °C for 1-2 hrs.
Working Area Large
Number of Labor 1
Comments ”Destruction of Asbestos fibers by sintering asbestos-volcanic tuff mixtures”, Ottavio Marino, Maria Palumbo, Giuseppe
Mascolo, Environmental Technology, Vol 16. pp. 89-94, [28]
Table 13: Conventional technology to destroy Asbestos
ASBESTOS
Items to compare
Conventional technology
Destruction technology
Hydrolysis between asbestos and supercritical steam at high temp and pressure
Efficiency 1
Amount of destruction
By Products Forsterite
Skilled Labor Yes to operate XRD,SEM and planetary grinding mill
Dangerous process
No but can become if the pressure exceeds safe limits in autoclave
Automatic Yes
111
PTOTMBD Yes as it is ground in a planetary grinding mill
Investment cost High because of XRD, SEM, autoclave
Running cost Low
Working Area Small area except the examination machines
Number of Labor 1
Comments ” Hydrothermal conversion of chrysotile asbestos using near supercritical conditions”, Kalliopi Anastasiadou, Dimosthenis
Axiotis, Evangelos Gidarakos, Journal of Hazardous Materials, [29]
Table 16: Conventional technology to destroy Chrysotile Asbestos
CHRYSOTILE ASBESTOS
Items to compare
Conventional technology
Destruction technology Thermal decomposition
Efficiency
Amount of destruction By Products Forsterite, Enstatite
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
Investment cost High because of ESEM, XRD
Running cost
Working Area
Number of Labor 1
Comments ”In situ ESEM study of the thermal decomposition of chrysotile asbestos in view of safe recycling of the transformation product”,
Alessandro F. Gualtieri, Magdalena Lassinantti Gualtieri, Massimo Tonelli, Journal of Hazardous Materials, [30]
Table 17: Conventional technology to destroy Asbestos
ASBESTOS
Items to compare
Conventional technology
Destruction technology Non-combustion mechano-chemical process
Efficiency 1
Amount of destruction By Products No
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
Investment cost High
Running cost High
112
Working Area Large
Number of Labor 1
Comments ”Safe Decomposition of Asbestos by Mechano-chemical Reaction”, Ryo Inoue, Junya Kano, Kaoru Shimme and Fumio Saito,
Materials Science Forum Vols. 561-565 pp. 2257-2260, [31]
Table 14: Conventional technology to destroy Asbestos
ASBESTOS
Items to compare
Conventional technology
Destruction technology Mechanochemical treatment
Efficiency
Amount of destruction By Products No
Skilled Labor Yes to operate planetary ball mill, XRD, SEM, phase contrast microscope
Dangerous process No
Automatic Yes
PTOTMBD No
Investment cost High because of SEM,XRD,phase-contrast microscope, Energy dispersion microanalysis
Running cost High
Working Area Large because of number of machines
Number of Labor 1
Comments ”Mechanochemical treatment to recycling asbestos- containing waste” P.Plescia, D.Gizzi, S. Benedetti, L.Camilucci, C.Fanizze,
P.DE Simone, F. Paglietti, Waste Management 23 (2003) 209-218, [32]
Table 19: Conventional technology to destroy Chrysotile
CHRYSOTILE
Items to compare
Conventional technology
Destruction technology
Low temperature decomposition of chrysotile asbestos by acidic gas formed by decomposition of Freon (by superheated steam at 150 °C for 30-60 mins)
Efficiency 99.99%
Amount of destruction
By Products Chrysotile fibers=No, Chrysotile containing slates=Quartz
Skilled Labor Yes for XRD, SEM, PCM
Dangerous process No
Automatic Yes
PTOTMBD No
Investment cost High
113
Running cost Low
Working Area Small
Number of Labor 1
Comments ”Low Temperature Decomposition of Chrysotile Asbestos by Freon-Decomposed Acidic Gas”, Takahiro Kozawa, Ayumum Onda,
Koji Kajiyoshi, Kazumichi, Yanagisawa, Junichi Shinohara, Tetsuro Takanami, Masatsugu Shiraishi and Masazumi Kanazawa,
Proceedings of International Symposium on Eco Topia Science 2007, ISETS07 (2007) , [33]
Table 20: Conventional technology to destroy Asbestos
ASBESTOS
Items to compare
Conventional technology
Destruction technology
Thermal decomposition of asbestos and recycling in traditional ceramics
Efficiency 100%
Amount of destruction
By Products Forsterite and Estatite
Skilled Labor Yes
Dangerous process
Automatic
PTOTMBD
Investment cost High
Running cost High
Working Area
Number of Labor 1
Comments ”Thermal decomposition of asbestos and recycling in traditional ceramics”, A.F. Gualtieri, A. Rartaglia, Journal of the European
Ceramic Society 20 (2000) 1409-1418, [34]
Table 21: Conventional technology to destroy Chrysotile Asbestos
CHRYSOTILE ASBESTOS
Items to compare
Conventional technology
Destruction technology Thermal decomposition
Efficiency 100%
Amount of destruction 100 g/3 hours
By Products Forsterite and Enstatite
Skilled Labor Yes for XRD, SEM, DTA, Thermogravimetric analysis
Dangerous process No
Automatic Yes
PTOTMBD No
Investment cost High because of XRD, SEM, DTA, Thermogravimetric analysis, box furnace
114
Running cost High as observations are made after coating the samples with thin layer of gold
Working Area Large area
Number of Labor 1
Comments ”Study on the thermal decomposition of chrysotile asbestos”, T.Zaremba, A.Krzakala, J. Piotrowski, D.Garczorz, Journal of
thermal analysis and calorimetry, [35]
2. Gases
2.1. NOx
Table 22: Conventional technology to destroy Nitric Oxide
NITRIC OXIDE
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of nitric oxide in oxygen rich gases using Cu ion-exchanged ZSM-5 zeolites
Efficiency 75%
Amount of destruction By Products N2
Skilled Labor No
Dangerous process No but care must be taken as it’s a high temp process
Automatic No
PTOTMBD No but the mixture was made before introducing it into the reactor
PTODABD Yes
Investment cost High because of muffle furnace, plasma emission spectrometer, electrically heated furnace, mass flow controller, NO-NOx analyzer
Running cost High because of high temperature operation
Working Area Large
Number of Labor 1
Comments ”Catalytic Decomposition of Nitric Oxide over Promoted Coper-Ion-Exchanged ZSM-5 Zeolites”, Yanping Zhang and Maria
Flytzani-Stephanopoulos, American Chemical Society, [36]
Table 23: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Decomposition of NOx with Low-temperature plasmas at atmospheric pressure: Neat and in the presence of oxidants, reductants, water and carbon dioxide
Efficiency > 90%
115
Amount of destruction By Products N2 , O2 and NO2 at low conversions
Skilled Labor No
Dangerous process No
Automatic No
PTOTMBD No but just a standard mixture is made
PTODABD No
Investment cost High
Running cost Low
Working Area Large
Number of Labor 1
Comments All quartz reactors have much higher efficiency than metal reactors of NOx decomposition
”Decomposition of Nox with Low-Temperature Plasmas at Atmospheric Pressure: Neat and in the Presence of Oxidants,
Reductants, Water and Carbon Dioxide”, Jian Luo, Steven L.Suib, Manuel Marquez,Yuji Hayashi and Hiroshige Matsumoto,
J.Phys.Chem.A 1998, 102, 7954-7963, [37]
Table 24: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology
Effective NOx decomposition and storage/reduction over mixed oxides derived from layered double hydroxides
Efficiency 55 – 75 %
Amount of destruction
By Products N2, O2
Skilled Labor No
Dangerous process
No but care must be taken as it’s a high temperature process
Automatic No
PTOTMBD No
PTODABD No but the catalysts are derived from precursors
Investment cost High
Running cost High
Working Area Small
Number of Labor
Comments ”Effective Nox decomposition and storage/reduction over mixed oxides derived from layered double hydroxides”, Jun Jie Yu. Xiao
Ping Wang, Yan Xin Tao, Zheng Ping Hao and Zhi Ping Xu, Ind.Eng.Chem.Res.2007, 46.5794-5797, [38]
Table 25: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
116
Destruction technology Decomposition of NO(x) using electrochemical reactor with a multilayer catalytic cathode
Efficiency 90%
Amount of destruction By Products NO, N2
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD No but just a standard mixture is made
PTODABD Yes in a way that the reactor is prepared with catalytic layers
Investment cost High
Running cost Low
Working Area
Number of Labor > 1
Comments Although in it’s called as a low temperature process but the high temperature is required for the preparation of catalysts
” Low Temperature NO(x) decomposition using electrochemical reactor”, K.Hamamoto, Y.Fujishiro, M.Awano, ECS Transactions,
11(33) 181-188 (2008) 10.1149/1.3038921, [39]
Table 26: Conventional technology to destroy NOx
NOX
Items to compare
Conventional technology
Destruction technology
Direct decomposition of NOx using catalysts at high temperature
Efficiency
Amount of destruction
By Products
Skilled Labor
Dangerous process
Automatic
PTOTMBD
PTODABD
Investment cost
Running cost
Working Area
Number of Labor
Comments It was all theoretical with the recommendations at the end for the conditions of preparation of model catalyst
”Fundamental study on the NO(x) direct decomposition catalysts”, Yasunori Yokomichi, toshiro Nakayama, Osamu Okada,
Yasuharu Yokoi, Iruru Takahashi, Hiroshi Uchida, Hideyuki Ishikawaka, Ryuichi Yamaguchi, Hisaji Matsui, tokio Yamabe,
Catalysis Today 29 (1996) 155-160, [40]
117
Table 27: Conventional technology to destroy NO2
NO2
Items to compare
Conventional technology
Destruction technology Photo dissociation of NO2 in the region 217-237 nm using a one-laser photo fragmentation/fragment-detection technique
Efficiency
Amount of destruction By Products
Skilled Labor
Dangerous process
Automatic
PTOTMBD
PTODABD
Investment cost
Running cost
Working Area
Number of Labor
Comments ”Photo dissociation of NO2 in the Region 217-237nm: Nascent NO Energy Distribution and Mechanism”, H.S. Im and E.R.
Bernstein, J.Phys.Chem.A 2002, 106, 7565-7572, [41]
Table 28: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Short duration of pulsed power to create streamer discharges
Efficiency
Amount of destruction 5000 Nm3/h
By Products HNO2, HNO3
Skilled Labor Yes
Dangerous process No but care is definitely required dealing with high voltage reactor
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High
Running cost Low
Working Area
Number of Labor 1
Comments The shorter the pulse width the higher the destruction efficiency ” Application of Pulsed Power for the Removal of Nitrogen Oxides from Polluted Air”, R.Hackam, H.Akiyama, IEEE Electrical
Insulation Magazine Vol.17, No.5, [42]
118
Table 29: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Decomposition using UV light
Efficiency Decreases with increasing removal rate
Amount of destruction By Products N2O, CO2
Skilled Labor No but just for analytical equipment
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High
Running cost Low
Working Area Lab Scale
Number of Labor 1
Comments ” An experimental study on photochemical effect of UV Light on NO(x) decompositions”, R.Sakuma, R.Ohyama, IEEE, Annual
Report Conference on Electrical Insulation and Dielectric Phenomena, [43]
Table 30: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Decomposition using electrochemical cell with a multi-layer cathode with high oxygen ion conducting materials
Efficiency 80%
Amount of destruction By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No but the reactor is prepared with the catalytic layers before destruction
Investment cost High
Running cost Low
Working Area
Number of Labor 1
Comments Decomposition temperature is above 550 °C ”Intermediate temperature electrochemical reactor for NO(x) decomposition”, K.Hamamoto, Y.Fujishiro, M.Awano, ECS
Transactions, 1(7) 389-396(2006) 10.1149/1.2215572, The Electrochemical Society, [44]
119
Table 31: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Plasma-assisted chemical reactor for NOx decomposition- Plasma combined with chemical scrubber, which uses 5% Na2SO3 as a chemical solution and will convert from NO2 to N2 and O2
Efficiency Nearly 100%
Amount of destruction By Products Minimum N2O formation and nontoxic Na2SO4
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD No but the gas mixture is made
PTODABD No
Investment cost High
Running cost Low
Working Area Lab Scale
Number of Labor 1
Comments ”Plasma-assisted chemical reactor for NO(x) decomposition”, Toshiaki Yamamoto, Chen-Lu Yang, Michael R.Beltran and Zhorzh
Kravets, IEEE Industry Application Society Annual Meeting, New Orleans, Louisiana, [45]
Table 32: Conventional technology to destroy NO
NO
Items to compare
Conventional technology
Destruction technology NO removal from a simulated combustion gas using the reciprocal pulse generator
Efficiency Low
Amount of destruction By Products Yes
Skilled Labor Yes
Dangerous process Yes
Automatic No but the gas mixture is made
PTOTMBD No
PTODABD
Investment cost Moderate
Running cost Low
Working Area Small
Number of Labor 1
Comments ”NO(x) decomposition with repetitive discharges caused by reciprocal voltage pulse in a coaxial cable”, K.Kadowaki, S.Nishimoto
and I.Kitani, [46]
120
Table 33: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Decomposition in simulated flue gases by means of a pulsed discharge plasma generated in a cylinder type reactor
Efficiency 65%
Amount of destruction 2 l/min
By Products N2O, NO2, O3, CH3COOH, CO2
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost Low
Working Area Large on lab scale
Number of Labor 1
Comments ” NO(x) removal process using pulsed discharge plasma”, Akira Mizuno, Kazuo Shimizu, Alokkumar Chakrabarti, Lucian
Dascalescu and Satoshi Furuta, IEEE Transactions on industry applications, Vol 32, no 5, September/October 1995, [47]
Table 34: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Decomposition using Xe discharge lamp as the vacuum UV source within a photochemical reactor
Efficiency Efficiency increases with increasing VUV radiated intensity
Amount of destruction By Products HNO3
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High
Running cost Low
Working Area Small
Number of Labor 1
Comments ” NO(x) treatment in Diesel Engineer Combustion Exhaust Gases by Vacuum Ultra-Violet Irradiation”, K.Ueno and R Ohyama,
2007 Annual Report Conference on Electrical Insulation and Dielectric Phenomena, [48]
121
Table 35: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Decomposition at 350-450 °C using a multi-layered electrochemical cell
Efficiency
Amount of destruction By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No but the catalytic layers are made before destruction
Investment cost High
Running cost Low
Working Area
Number of Labor 1
Comments ”Multilayered electrochemical cell fro NO(x) decomposition at moderate temperatures”, Vitali Sinitsyn, Koichi Hamamoto,
Yoshinobo Fujishiro, Sergei Bredikhin, Masanobu Awano, Ionics (2006) 12: 211-213, DOI: 10.1007/s11581-006-0030-6, [49]
Table 36: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Decomposition using pulsed microwave discharges at atmospheric pressure
Efficiency 95%
Amount of destruction By Products NO2 production is reduced
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No but the gas mixture is made
PTODABD No
Investment cost High
Running cost Low
Working Area Small
Number of Labor 1
Comments ”Pulsed microwave discharge at atmospheric pressure for NO(x) decomposition”, M Baeva, H Gier, A Pott, J Uhlenbusch, J
Hoschele and J Steinwandel, Plasma Sources Sci, Technol. 11(2002) 1-9, [50]
122
Table 37: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Destruction using microwave and electron beam processing
Efficiency 55% only with microwave processing but MW and EB increase it up to 95%
Amount of destruction By Products NH4NO3
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD No but the gas mixture is made
PTODABD No
Investment cost High because of gaseous mixture preparation system, microwave source, electron beam source, multimode rectangular cavity
Running cost Low
Working Area Large on lab scale
Number of Labor 1
Comments This process enable simultaneous removal of NOx and SO2 ”SO2 and Nox removal by microwave and electron beam processing”, Daneil Lghigeanu, Ioan Calinescu, Diana Martin,
Constantin Materi, Anca Bulearca, Adelina Ighigeanu, Journal of Microwave Power and Electromagnetic energy 43, No 1, 2009,
[51]
Table 38: Conventional technology to destroy NOx
NOx
Items to compare
Conventional technology
Destruction technology Adsorption, desorption followed by non-thermal plasma decomposition
Efficiency 90%
Amount of destruction Different flow rates were used, 1 L/min,2 L/min
By Products
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost Moderate
Running cost Low
Working Area Small
Number of Labor 1
Comments Cost efficient technology
123
”Nobel Nox and VOC Treatment using concentration and Plasma decomposition”, Toshiaki Yamamoto, Souma Asada, Tomohiro
Lida and Yoshiyasu Ehara, IEEE 978-1-4244-6395-4/10, [52]
2.2. CFC
Table 39: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Catalytic hydrolysis of CFC-12 over WO3/SnO2 solid acid
Efficiency 99.50%
Amount of destruction By Products CFC-13
Skilled Labor Skilled person for X-ray diffractometer
Dangerous process Yes, as CFC-13 is released
Automatic No
PTOTMBD No
PTODABD
Investment cost High because of X-ray diffractometer
Running cost High because it is a high temperature process
Working Area Small
Number of Labor 1
Comments No deactivation of catalysis during whole process ”A novel CFC-12 Hydrolysis Catalyst: WO3/SnO2”, Zhen MA, Wei Ming HUA, Yi TANG, Zi GAO, Chinese Chemical Letters Vol. 11,
No.1, pp. 87-88, 2000, [53]
Table 40: Conventional technology to destroy CFC-13
CFC-13
Items to compare
Conventional technology
Destruction technology Decomposition by non-thermal plasma chemical decomposition technology using ferroelectric plasma reactor
Efficiency 95% with 0.5 L/min and 86% with 1 L/min
Amount of destruction
By Products Different by-products for different background gases, e.g. CHCl2F, CHCl3, CHClF2 , CCl3F, CCl2F2, CH2ClF, CCl2F2, C2H5Cl, C2H5Cl
Skilled Labor Yes
Dangerous process Yes as dangerous by-products are released
Automatic Yes
PTOTMBD No
PTODABD
Investment cost High due to flame ionization detector, gas chromatograph detector, Laser aerosol spectrometer, ferroelectric plasma reactor
124
Running cost Low
Working Area Small as it’s laboratory scale
Number of Labor 1
Comments By products were high for dry H2 followed by dry N2, wet N2, wet air and dry air
”Aerosol Generation and Decomposition of CFC-113 by the Ferroelectric Plasma Reactor”, Toshiaki Yamamoto, Ben W.L. Jang,
IEEE Transactions on Industry applications, Vol 34, No.4, July/August 1999, [54]
Table 41: Conventional technology to destroy CFC-112 and CFC-113
CFC-112 and CFC-113
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of CFC-112 and CFC-113 in the presence of ethanol with iron(3) chloride catalyst supported on active charcoal at low temperature
Efficiency
Amount of destruction Decreases with time
By Products For CFC-112( C2F2Cl2, CHFClCFCl2,CFCl2CFCl2) For CFC-113 (C2F3Cl, C2F2Cl2, CHFClCF2Cl,CF2ClCFCl2)
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD
Investment cost Low
Running cost Low
Working Area Small
Number of Labor 1
Comments It is a low temperature process ”Catalytic Decomposition of CFC-112 and CFC-113 in the presence of Ethanol”, Daisaku MIYATANI, Kiyonori SHINODA, Tadashi
NAKAMURA, Minoru OTHA and Kensei YASUDA, The Chemical Society of Japan Chemistry Letters, pp. 795-798, 1992, [55]
Table 42: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of CFC-12 using Mo2O3/ZrO2 as catalyst with varying ZrO2 content in the presence of water vapor and oxygen
Efficiency
Amount of destruction
By Products CClF3
Skilled Labor Yes
Dangerous process No
125
Automatic Yes
PTOTMBD No
PTODABD
Investment cost High because of X-ray diffractometer, fixed bed reactor, tubular flow reactor made of stainless steel, gas chromatograph, mass spectrometer, Carlo Erba analyzer
Running cost High
Working Area Large
Number of Labor 1
Comments Very long process, took 100 hours Catalytic decomposition of CFC-12 over Solid Super Acid Mo2O3/ZrO2, Ping Ning, Xianyu Wang, Hasn-Jorg bart, Tiancheng Liu,
Jun Huang, Yaming Wang and Hong Gao, Journal of Environmental Engineering, Vol. 136, No.12 December 2010, pp. 1418-1423,
doi 10.1061/(ASCE) EE. 1943-7870.0000287, [56]
Table 43: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Decomposition of CFC-12 using WO3/TiO2 catalysis in the presence of water vapors
Efficiency 99.80%
Amount of destruction
By Products CFC-13 (very little)
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD
Investment cost Low
Running cost Low
Working Area Small
Number of Labor 1
Comments ”Catalytic decomposition of CFC-12 over WO3/TiO2”, Zhen MA, Weiming Hua, Yi Tang and Zi Gao, Chemistry Letters, [57]
Table 44: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of CFC-12 in the presence of water vapors over a series of solid acids WO3/ZrO2
Efficiency 98%
Amount of destruction
By Products
126
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD
Investment cost High because of X-ray diffractometer, gas chromatography
Running cost High because of calcinations
Working Area Small
Number of Labor 1
Comments In other decomposition of processes of HF and HCl are produced which corrode the catalyst but in this reaction HF and HCl are neutralized
”Catalytic hydrolysis of chlorofluorocarbon (CFC-12) over WO3/ZrO2”, Weiming Hua, Feng Zhang, Zhen Ma, Yi Tang and Zi Gao,
Chemistry Letters 65 (2000) 85-89, [58]
Table 45: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Destruction of CFC-11 using moderate power microwave torch discharge in atmospheric pressure flowing nitrogen
Efficiency 100%
Amount of destruction 300 g/h
By Products No unwanted by products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD
Investment cost High but a low cost prototype is proposed
Running cost Not that high
Working Area Small
Number of Labor 1
Comments Superior than other methods as there is no generation of any unwanted by-products plus 100% efficiency
”CFC-11 destruction by microwave torch generated atmospheric-pressure nitrogen discharge”, Mariusz Jasinski, Jerzy
Mizeraczyk, Zenon Zakrzewski, Toshikazu Ohkubo and Jen-Shih Chang, Journal of Physics D: Applied Physics. 35(2002) 2274-
2280, [59]
Table 46: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Decomposition of CFC12 using shell wastes by direct reaction
127
between CFC12 and alkaline based materials at low temperatures
Efficiency 99.9%
Amount of destruction
By Products CCl3F,CCl2F2,CClF3
Skilled Labor Yes
Dangerous process No but plant can cause problems if not handled with care
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High as calcination at high temperature is required in start for 12 hours, fluorescence spectrometer, thermo gravimetric analyzer, SEM
Running cost High
Working Area Large
Number of Labor > 1
Comments ”CFC12 Decomposition over Shell Wastes Based Reactants”, Yoshiki Kawamoto, Daisuke Hirabayashi, Kenzi Suzuki, Hideki
Inagaki, Akihiro Takeuchi, Chouyuu Watanabe, Proceedings of International Symposium on Eco Topia Science 2007,
ISETS07(2007) , [60]
Table 47: Conventional technology to destroy CFCs
CFCs
Items to compare
Conventional technology
Destruction technology Complete destruction of CFCs by reductive dehalogenation using sodium naphthalenide
Efficiency > 99%
Amount of destruction
By Products No
Skilled Labor Yes for x-ray analysis
Dangerous process No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost High but can be reduced
Working Area Small
Number of Labor 1
Comments ”Complete Destruction of Chlorofluorocarbons by Reductive Dehalogenation Using Sodium Naphthalenide”, Akira Oku, Kenji
Kumura and Masaya Sato, Ind. Eng. Chem. Res. 1989, 28, 1055-1059, [61]
Table 48: Conventional technology to destroy CFC Gases
CFC GASES
128
Items to compare
Conventional technology
Destruction technology Decomposition of CFC gases by surface discharge induced plasma chemical processing in atmospheric air, pure oxygen gas or pure nitrogen gas
Efficiency 90% for CFC-22 and 99% for CFC-113
Amount of destruction
By Products
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost Not high but a bit expensive
Running cost Low
Working Area Small
Number of Labor 1
Comments ”Decomposition of Fluorocarbon Gaseous Contaminants by Surface Discharge-Induced Plasma Chemical Processing”, Tetsuji
Oda, Tadashi Takahashi, Hiroshi Nakano, Senichi Masuda, IEEE Transactions on Industry Applications, Vol 29, No.4, July/August
1993, [62]
Table 49: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Decomposition of CFC-12 by adding hydrogen in a cold plasma system
Efficiency > 95%
Amount of destruction
By Products CH4,C2H2, HCl, HF, SiF4
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High because of spectrometer, FTIR, Plasma reactor
Running cost Low
Working Area Large
Number of Labor 1
Comments ”Decomposition of Dichlorodifluoromethane by Adding Hydrogen in a Cold Plasma System”, Ya Fen Wang, Wen Jhy Lee, Chuh
Yung Chen, Lien Te Hsieh, Environmental Science Technology 1999, 33, 2234-2240, [63]
129
Table 50: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of CFC-12 on TiO2/SiO2
Efficiency > 97%
Amount of destruction
By Products CH4
Skilled Labor Yes for analysis
Dangerous process No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High because of X-ray diffractometer, Spectrophotometer
Running cost High
Working Area Large
Number of Labor 1
Comments ”Decomposition of Dichlorodifluoromethane on TiO2/SiO2”, Seiichiro Imamura, Toshihiko Shiomi, Shingo Ishida, Kazunori Utani,
Hitoshi Jindai, Ind. Eng. Chem. Res. 1990, 29, 1758-1761, [64]
Table 51: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Decomposition of CFC-12 by surface discharge induced plasma chemical process using a reactor
Efficiency 92.70%
Amount of destruction
By Products
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High
Running cost Low
Working Area Small
Number of Labor 1
Comments Decomposition efficiency increases with time ”Decomposition of Chlorofluorocarbon by Non-thermal Plasma”, Hyun-Choon Kang, J.Ind. Eng. Chem, Vol., No.5, (2202) 488-
492, [65]
130
Table 52: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Decomposition of CFC-12 by 12 kind of metal supported gas diffusion electrodes causing defluorination and dechloroination
Efficiency 100%
Amount of destruction
By Products HFC-32,CH4, C2H4, C2H6, H2, CHClF2,CH2F2
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High
Running cost Low
Working Area Small
Number of Labor 1
Comments ”Electrochemical Decomposition of CFC-12 Using Gas Diffusion Electrodes”, Noriyuki Sonoyama and Tadayoshi Sakata, Environ.
Sci. Technol. 1998, 32, 375-378, [66]
Table 53: Conventional technology to destroy CFCs
CFCs
Items to compare
Conventional technology
Destruction technology Decomposition of chlorofluorocarbons by water plasma
Efficiency
Amount of destruction
By Products Cl2
Skilled Labor
Dangerous process
Automatic
PTOTMBD No
PTODABD No
Investment cost High
Running cost High
Working Area
Number of Labor
Comments High temperature process, so very expensive ”Thermodynamic consideration of the water plasma decomposition process of chlorofluorocarbons”, S Takeuchi, M Itoht, K
Takeda, K Mizuno, T Asakuras and A Kobayashi, Plasma Sources Sci. Technol. 2 (1993) 63-66, [67]
131
Table 54: Conventional technology to destroy CFC-13
CFC-13
Items to compare
Conventional technology
Destruction technology Decomposition of CFC-13 with 13 kinds of metal supported porous carbon diffusion electrodes by dechlorination and defluorination
Efficiency 77.70%
Amount of destruction
By Products CH4, HFC-23
Skilled Labor No
Dangerous process Yes because of HFC-23
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High
Running cost Low
Working Area Small
Number of Labor 1
Comments ”Electrochemical Hydrogenation of CFC-13 Using Metal-Supported Gas diffusion electrodes”, Noriyuki Sonoyama and tadayoshi
Sakata, Environ. Sci, Technol. 1998, 32, 4005-4009, [68]
Table 55: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Hydrolytic decomposition of CFC-12 on modified ZrO surfaces and charcoal at 450 °C
Efficiency 100%
Amount of destruction
By Products CO2, HCl, HF, CFC-13
Skilled Labor No
Dangerous process Yes
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost High
Working Area Small
Number of Labor 1
Comments Recommended only where condensation procedures due to low CFC concentration are too expensive
132
”Heterogeneously catalyzed hydrolytic decomposition of CFCS”, Kai-Uwe Niedersen, Lefriede Lieske and Erhard Kemnitz, Green
Chemistry October 1999, [69]
Table 56: Conventional technology to destroy CFC
CFC
Items to compare
Conventional technology
Destruction technology Decomposition of CFC in the troposphere with the aid of natural lightning
Efficiency
Amount of destruction 900 kg/yr.
By Products
Skilled Labor No
Dangerous process No
Automatic No
PTOTMBD No
PTODABD No
Investment cost High
Running cost High
Working Area Very large
Number of Labor More than 1
Comments CFC production rate is 800 tons/year and lightning decompose only 930 kg/year
”The decomposition of CFCs in the troposphere by lightning”, Mengu Cho and Michael J. Rycroft, Journal of Atmospheric and
Solar Terrestrial Physics Vol.59, No.12, pp. 1373- 1379, 1997, [70]
Table 57: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology
Hydrolytic decomposition of CFC-12 on various method Zirconium oxide surfaces at 500 °C
Efficiency > 90%
Amount of destruction
By Products Limited formation of CFC-13,CFC-12,CO2
Skilled Labor Yes
Dangerous process Yes
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High due to XRD, FTIR, Spectrometer, autoclave
Running cost High as it is a high temperature process
Working Area Large because of XRD and spectrometer
133
Number of Labor 1
Comments Deactivation of catalysis after long time operation ”Hydrolytic decomposition of dichlorodifluoromethane on modified zirconium oxide surfaces”, A. Hess and E. Kemnitz, Catalysis
Letters 49 (1997) 199-205, [71]
Table 58: Conventional technology to destroy CFC-11 and CFC-113
CFC-11 and CFC-113
Items to compare
Conventional technology
Destruction technology Sonochemical destruction of CFC-11 and CFC-113 in dilute aqueous solution using ultrasonic energy
Efficiency > 90%
Amount of destruction 23 mg/6 mins for batch process, 38 mg/30 mins for circulating process Kg/s
By Products HF, HCl
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD No but like most of the processes a solution is made with water
PTODABD No
Investment cost High
Running cost Low
Working Area Couldn’t be judged
Number of Labor 1
Comments This approach does not require transference of target molecule from an aqueous phase as would be required in combustion, catalytic or otherwise
”Sonochemcial Destruction of CFC-11 and CFC-13 in dilute aqueous solution”, H, Michael Cheung and Shreekumar Kurup,
Environ. Sci. Technol. 1994, 28, 1619-1622, [72]
Table 59: Conventional technology to destroy CFC
CFC
Items to compare
Conventional technology
Destruction technology
CFC decomposition caused by energy transfer from electronically excited species within a non-thermal plasma in nitrogen at atmospheric pressure
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process Yes
Automatic Yes
134
PTOTMBD No
PTODABD No
Investment cost High because of electrical discharge reactor, gas analyzer, soap film flow meter, oscillator, high voltage amplifier, electric furnace, positive generator, FTIR spectrometer
Running cost High because of electric furnace operation
Working Area Large
Number of Labor 1
Comments ”Mechanism of the Dissociation of Chlorofluorocarbons during No thermal Plasma Processing in Nitrogen at Atmospheric
Pressure”, Arkadiy Gal, Atsushi Ogata, Shigeru Futamura and Koichi Mizuno, J.Phys. Chem. A 2003, 107, 8859-8866, [73]
Table 60: Conventional technology to destroy CFC-12
CFC-12
Items to compare
Conventional technology
Destruction technology Non-thermal atmospheric pressure plasma with TiO2 catalyst combination to decompose CFC-12 in nitrogen and air
Efficiency
Amount of destruction
By Products CO,CO2,COF2,HCl,N2O for Nitrogen gas streams and CO,CO2,COF2,HCOCl,NO,NO2,N2O in air
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High because of plasma rector, oscilloscope, mass flow controller, FTIR spectrometer
Running cost High but not that much
Working Area Large
Number of Labor 1
Comments ”Plasma-assisted catalysis for the destruction of CFC-12 in atmospheric pressure gas steams using TiO2”, Anna E. Waalis, J.
Christopher Whitehead, Kui Zhang, Catalysis Letters vol. 113 Nos. 1-2, January 2007, DOI: 10.1007/s 10562-006-9000-x, [74]
Table 61: Conventional technology to destroy Freon-12
Freon-12
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of Freon-12 on BPO4 catalyst
Efficiency 100%
Amount of destruction
By Products CO2
135
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High because of electron spectroscopy, X-ray diffractometer, SEM
Running cost High
Working Area Large
Number of Labor 1
Comments BPO4 is the highest durable catalyst but it was deactivated during the prolong use, it’s efficiency can be improved by using CaO which saves it from poisoning from inorganic fluorine’s
” Decomposition of Dichlorodifluoromethane on BPO4 Catalyst” Henrik K.Hansen, Peter Rasmusen, Aage Fredenslund, Martin
Schiller, Jurgen Gmehling, Ind. Eng. Chem. Res. 1991, 30, 2355-2358, [75]
Table 62: Conventional technology to destroy CFC
CFC
Items to compare
Conventional technology
Destruction technology Decomposition in presence of water over different catalysts in which TiO2-ZrO2 had highest activity
Efficiency 100%
Amount of destruction
By Products CFC, HCF, CO, CO2
Skilled Labor Yes
Dangerous process No, specially HF and HCl are removed in the reaction which is a big advantage
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High because of XRD, gas chromatographer, spectrophotometer
Running cost High
Working Area Large
Number of Labor 1
Comments ” Decomposition of Chlorofluorocarbones on TiO2-ZrO2”, Masahiro Tajima, Mki Niwa, Yasushi Fujii, Yutaka Koinuma, Reiji
Aizawa, Satoshi Kushiyama, Satoru Kobayashi, Koici Mizuno, ideo Ohuchi, [76]
Table 63: Conventional technology to destroy CFCs,
CFCs
Items to compare
Conventional technology
Destruction technology Decomposition of CFCs in the presence of water over different solid acid catalysts
136
Efficiency 40%
Amount of destruction
By Products CFCs, CO, CO2
Skilled Labor Yes but for analytical tools but not for experimentation
Dangerous process Yes
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost High
Working Area Large
Number of Labor 1
Comments HCl and HF produced are easily removed by neutralization ”Decomposition of chlorofluorocarbonsn in the presence of water over zeolite catalyst”, Masahiro Tajima, Miki Niwa, Yasushi
Fujii, Yutaka Koinuma, Reiji Aizawa, Satoshi, Kushiyama, Satoru Kobayashi, Koichi Mizuno, Hideo Ohuchi [77]
2.3. HCFC
Table 64: Conventional technology to destroy HCFC-22
HCFC-22
Items to compare
Conventional technology
Destruction technology
Catalytic decomposition of HCFC-22 by adding platinum to sulfated and non-sulfated TiO2-ZrO2 mixed oxides
Efficiency 90%
Amount of destruction
By Products CHClF2, CO, CO2, CHF3, HCl, HF
Skilled Labor Yes
Dangerous process
No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High because of diffractometer and spectrometer
Running cost High because of high temperature and long process
Working Area Large
Number of Labor 1
Comments ”Catalytic decomposition of chlorodifluoro methane (HCFC-22) over platinum supported on TiO2-ZrO2 mixed oxides”, Hongxia
Zhang, Ching Fai Ng, Suk Yin Lai, Applied Catalysis B: Environmental 55 (2005) 301-307, [78]
Table 65: Conventional technology to destroy HCFC-123 and HCFC-141b
HCFC-123 and HCFC-141b
137
Items to compare
Conventional technology
Destruction technology Decomposition by Chlorine as oxidizing agent
Efficiency
Amount of destruction
By Products CF3C(O)Cl, COFCl, CO
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High because of spectrometer, interferometer, Mercury-Cadmium-tellurdie detector, heat gun, ultraviolet lamps, infra-red source
Running cost Low
Working Area Large
Number of Labor 1
Comments ” Chlorine Initiated Oxidation Studies of Hydro chlorofluorocarbons: Results of HCFC-123 (CF3CHCl2) and HCFC-141b (CFCl2CH3),
E.O. Edney, B.W. Gay Jr and D.J. Driscoll, Journal of Atmospheric Chemistry 12: 105-120, 1991, [79]
Table 66: Conventional technology to destroy HCFCs and HCFs
HCFCs and HCFs
Items to compare
Conventional technology
Destruction technology Photochemical oxidation studies by chlorine initiated photo oxidation
Efficiency
Amount of destruction
By Products C(O)F2,HFC(O),CF3CF(O),C(O)F2,HFC(O),CF3CF(O),C(O)F2,C(O)F2
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High because of spectrometer, interferometer, Mercury-Cadmium-Telluride detector, heat gun, UV lamps, infrared source
Running cost Low
Working Area Large
Number of Labor 1
Comments Chlorine Initiated Photooxidation Studies of Hydrochlorofluorocarbons(HCFCs) and Hydrofluorocarbons(HFCs): Results for HCFC-
22(CHClF2);HFC-41(CH3F);HCFC-124(CClFHCF3);HFC-125(CF3CHF2);HFC-134a(CF3CH2F);HCFC-142b(CCLF2CH2); and HFC-
152A(CHF2CH3) , [80]
138
Table 67: Conventional technology to destroy CFCs and HCFCs
CFCs and HCFCs
Items to compare
Conventional technology
Destruction technology Decomposition in water by ultrasonic radiation
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost Low
Working Area
Number of Labor 1
Comments ”Decomposition of Chlorofluorocarbons and hydrofluorcarbons in water by ultrasonic irradiation”, K.Hirai, Y.Nagata, Y. Maeda,
Ultrasonics Sonochemistry 3 (1996) S205-S207, [81]
Table 68: Conventional technology to destroy HCFC-22
HCFC-22
Items to compare
Conventional technology
Destruction technology Catalytic decomposition by using gold nano particles and TiO2-ZrO2 as catalyst
Efficiency 100% can be achieved by increasing temperature
Amount of destruction
By Products HF, HCl,CO,CO2,CHClF2,CHF3
Skilled Labor No
Dangerous process Yes
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost Low
Working Area Small
Number of Labor 1
Comments Gold nano particles are catalytically active from CO oxidation ”Deactivation of gold catalysts supported on sulfated TiO2-ZrO2 mixed oxides for CO oxidation during catalytic decomposition of
chlorodifluoromethane (HCFC), Suk Yin Lai, Hongxia Zhang and Ching Fai Ng, Catalysis Letters Vol. 92, Nos. 3-4, February 2004,
[82]
139
Table 69: Conventional technology to destroy HCFC-22
HCFC-22
Items to compare
Conventional technology
Destruction technology Decomposition by using cold plasma controlled by pulse high voltage apparatus
Efficiency 97%
Amount of destruction
By Products HF
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost Moderate
Running cost Low
Working Area Small
Number of Labor 1
Comments ”Decomposition of HCFC-22 in a cold plasma system”, Shinya Hayashi, Takaki Inaoka, Wataru Minami, Hee-Joon Kim,
Department of Ecological Engineering, Toyohashi University of Technology Japan, [83]
Table 70: Conventional technology to destroy CHF2Cl
CHF2Cl
Items to compare
Conventional technology
Destruction technology Decomposition of CHF2Cl in a non-thermal atmospheric pressure plasma reactor with a perforated dielectric barrier
Efficiency Depends upon various factors Max 62% Min 5%
Amount of destruction
By Products CO2, N2O, CO, COF2, NO2
Skilled Labor Yes
Dangerous process Yes
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High because of FTIR, spectrometer, transformer, oscilloscope
Running cost Low
Working Area Small
Number of Labor 1
Comments
140
”Destruction of Chlorodifluoromethane(CHF2Cl) by Using Dielectric Barrier Discharge Plasma”, Young Sun Mok, Sang-Baek Lee
and Myung Shik Chang, IEEE Transactions on plasma science, Vol.37, no.3, March 2009, [84]
Table 71: Conventional technology to destroy CF2HCl
CF2HCl
Items to compare
Conventional technology
Destruction technology Decomposition by pyrolysis at 670-750 °C
Efficiency
Amount of destruction
By Products HF, HCl, C2F4, CF2HCl
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost High
Working Area Lab Scale
Number of Labor 1
Comments Thermal decomposition processes are very expensive for all toxic material decomposition
”The thermal decomposition of chlorodifluoromethane”, F.Gozzo, C.R. Patrick, Tetrahedron, 1966, Vol.22, pp. 3329-3336, [85]
Table 72: Conventional technology to destroy CHClF2
CHClF2
Items to compare
Conventional technology
Destruction technology Decomposition under non-equilibrium oxidizing plasma conditions
Efficiency .99 conversion
Amount of destruction
By Products CO, Cl, F, CCl2F2, CClF3
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High
Running cost Low
Working Area Lab Scale/Medium
Number of Labor 1
Comments
141
”Plasma-induced decomposition of chlorodifluoromethan”, Anna Opalska, Teresa Opalinska, Jerzy Polaczek, Pawel Ochman,
Instytut Chemii Przemyslowej, Rydygiera 8, 01-793 Warsaw, POLAND, [86]
Table 73: Conventional technology to destroy Hydrogenolyzing
HYDROGENOLYZING
Items to compare
Conventional technology
Destruction technology Decomposition of hydrogenolyzing in presence of RhCl3(py)3 and other homogeneous catalysts
Efficiency 96.5% max
Amount of destruction
By Products CHF3, CH4, are main products, CHF2Cl, CH2F2, NH3C2H6
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High because of different spectrometer, gas chromatographs, autoclave
Running cost Low
Working Area Large
Number of Labor 1
Comments ”Homogeneous catalytic hydrogenolysis of chlorodifluoromethane”, Otoo Balazs Simon, Attila Sisak, Applied Catalysis A: General
342(2008) 131-136, [87]
Table 74: Conventional technology to destroy Freon21 and Freon-142-B
FREON21 and FREON-142-B
Items to compare
Conventional technology
Destruction technology Decomposition of Freon 21 and Freon 142-B using high-voltage glow discharge plasma
Efficiency 100% by using higher voltages
Amount of destruction
By Products CO2, HF, Cl, HCl, CO
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost Low
Working Area Small
Number of Labor 1
142
Comments ”Destruction of Freons by the Use of High-Voltage Glow Plasmas”, Franz-Josef Spiess, Xiao Chen, Stephanie L.Brock, Steven
L.Suib, Yuji Hayashi and Hiroshige Matsumoto, J.Phys. Chem. A 2000, 104, 11111-11120, [88]
Table 75: Conventional technology to destroy HCFC-22
HCFC-22
Items to compare
Conventional technology
Destruction technology Electrochemical hydrogenation of HCFC-22 using metal and metal-phthalocyanine supported gas diffusion electrodes and only Co-PC GDE showed catalytic activity for HCFC-22 hydrogenation
Efficiency Increases with negative increase in potential during electrolysis
Amount of destruction
By Products CH4, HFC-32
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost Moderate
Running cost Moderate
Working Area Small
Number of Labor 1
Comments ”Electrochemical hydrogenation of chlorodifluoromethane (HCFC-22) at metal and metal-phthalocyanine-supported gas
diffusion electrodes”, Noriyuki Sonoyama, Tadayoshi Sakata, Advances in Environmental Research 8 (2004) 287-291, [89]
Table 76: Conventional technology to destroy Carbon-12 Substituted Chlorodifluoromethane
CARBON-12 SUBSTITUTED CHLORODIFLUOROMETHANE
Items to compare
Conventional technology
Destruction technology Infrared multi-photon produced through CO2 laser pulse used for decomposition of carbon-13 substituted chlorodifluoromethane molecules
Efficiency
Amount of destruction
By Products C2F4
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost Low
143
Working Area Small
Number of Labor 1
Comments ”Efficient Production of C2F4 in the Infrared Laser Photolysis of CHClF2”, M.Gauthier, C.G. Cureton, P.A. Hackett and C.Willis,
Appl. Phys. B 28, 43-50, 1982, [90]
3. Liquids
3.1. Acids
Table 77: Conventional technology to destroy Hydrogen Iodide
HYDROGEN IODIDE
Items to compare
Conventional technology
Destruction technology
Decomposition of HI using a fixed bed reactor in the range of 523-823 K using Pt/C catalysts
Efficiency 25%
Amount of destruction
By Products
Skilled Labor Yes but for analytical instruments
Dangerous process
No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High as SEM, EDS and XRD analysis were carried out
Running cost High as it’s a high temperature process because of pre-treatment of toxic material
Working Area Large
Number of Labor 1
Comments ”Decomposition of hydrogen iodide on Pt/C-based catalysts for hydrogen production”, Jung-Min Kim, Jung-Eun Park, Young-Ho
Kim, Kyoung-Soo Kang, Chang-Hee Kim, Chu-Sik Park, Ki-Kwang Bae, International Journal of hydrogen energy 33 (2008) 4974-
4980, [91]
Table 78: Conventional technology to destroy Oxalic Acid
OXALIC ACID
Items to compare
Conventional technology
Destruction technology
Decomposition of oxalic acid with HNO3 in the presence of Mn2+ ions by reacting KMnO4 and oxalic acid
Efficiency 99.90%
Amount of
144
destruction
By Products
Skilled Labor No
Dangerous process No
Automatic No
PTOTMBD No
PTODABD No
Investment cost Low
Running cost Low
Working Area Small
Number of Labor 1
Comments ”Decomposition of oxalic acid with nitric acid”, M.Kubota, Journal of Radioanalytical Chemistry Vol.75, No’s 1-2 (1982) 39-49,
[92]
Table 79: Conventional technology to destroy Formic Acid
FORMIC ACID
Items to compare
Conventional technology
Destruction technology
Decomposition of formic acid using clean and partially oxidized surfaces by temperature programmed reaction spectroscopy
Efficiency
Amount of destruction
By Products CO2, CO, H2
Skilled Labor Yes
Dangerous process
No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost Moderate
Working Area
Number of Labor 1
Comments ”Formic acid decomposition from clean and oxidized nickel/iron(100) alloy surfaces”, E.M. Silverman and R.J. Madix, C.R.
Brundle, J. Vac. Sci. Technol. 18(2), March 1981, [93]
Table 80: Conventional technology to destroy Nitric Acid
NITRIC ACID
Items to compare
Conventional technology
Destruction Decomposition of nitric acid vapor at low pressures in two vycor bulbs at
145
technology temp b/w 375-424 with and without addition of argon, CO2, oxygen, water, nitrogen oxide and nitric oxide
Efficiency Nearly 100%
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process Yes
Automatic No
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost Low
Working Area Small
Number of Labor 1
Comments ”Kinetic of the thermal decomposition of nitric acid vapor 3. Low pressure results”, Harold S. Johnston, Lousie Foering, James
R.White, J.Am. Chem. Soc. 1955, 77(16), pp. 4208-4212, [94]
Table 81: Conventional technology to destroy Hydrogen Iodide
HYDROGEN IODIDE
Items to compare
Conventional technology
Destruction technology Destruction of HI using Ni catalysts
Efficiency
Amount of destruction 0.1 mL/min
By Products NI2 which causes the deactivation of catalyst
Skilled Labor No
Dangerous process
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost High because it’s a high temperature process and catalyst preparation
Working Area Small
Number of Labor 1
Comments ”Ni catalyst deactivation in the reaction of hydrogen iodide decomposition”, Favuzza P, Felici C, Mazzocchia C. Spadoni A.
Tarquini P. Tito A.C., AIDIC Conference Series, Vol. 9,2009 DOI: 10.3303/ACOS0909016, [95]
Table 82: Conventional technology to destroy Hydrogen Peroxide
HYDROGEN PEROXIDE
Items to compare
Conventional technology
146
Destruction technology Decomposition by peroxocarbonic acid anion
Efficiency
Amount of destruction
By Products
Skilled Labor No
Dangerous process No
Automatic No
PTOTMBD No
PTODABD No
Investment cost High because of spectrometer, deinking mill
Running cost Low
Working Area Small
Number of Labor 1
Comments ”On the decomposition of hydrogen peroxide via the peroxocarbonic acid anion”, Dr. H.U. Suess, Dr. M. Janik, Technical
association of the pulp and paper industry of southern Africa, [96]
Table 83: Conventional technology to destroy Acetic Acid
ACETIC ACID
Items to compare
Conventional technology
Destruction technology
Photo catalytic decomposition on TiO2 in an inert atmosphere by two parallel path ways at room temperature
Efficiency
Amount of destruction
By Products CO2, C2H6, CH4, H2O
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High because of UV lamps, radiometer, pyrex reactor, mass spectrometer
Running cost High as the reactor is maintained at 723 K for 30 mins before the start of each experiment
Working Area Small
Number of Labor 1
Comments In first pathway lattice oxygen is required but not in the second pathway ”Photo catalytic decomposition of acetic acid on TiO2”, Darrin S. Muggli, Sarah A. Keyser and John L. Falconer, Catalysis Letters
55 (1998) 129-132, [97]
Table 84: Conventional technology to destroy Boric Acid
BORIC ACID
Items to compare
Conventional technology
147
Destruction technology Decomposition through pressure induced chemical decomposition
Efficiency
Amount of destruction
By Products Cubic metabolic acid (HBO2)
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High because of X-ray powder diffraction, infrared spectroscopy measurements
Running cost Low
Working Area Large
Number of Labor 1
Comments ”Structural changes and pressure-induced chemical decomposition of boric acid”, A. Yu. Kuznetsov, A.S. Pereira, J. Haines, L.
Dubrovinsky, V. Dmitriev, P. Pattision, Joint 20th
Airapt- 43th EHPRG, June 27-July 1, Karlsruhe/ Germany 2005, [98]
Table 85: Conventional technology to destroy Nucleic Acids
NUCELIC ACIDS
Items to compare
Conventional technology
Destruction technology Selective decomposition by high temperature and pressure region around a gold nanoparticle, generated when a gold nano-particle was irradiated with a pulsed laser in aqueous solution
Efficiency 100%
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost High
Working Area
Number of Labor 1
Comments ” Selective decomposition of nucleic acids by laser irradiation on probe-tethered gold nanoparticles in solution”, Yoshihiro
Takeda, Tamotsu Kondow and Fumitaka Mafune, Physics Chemistry Chemical Physics, DOI: 10.1039/c0cp00770f, [99]
Table 86: Conventional technology to destroy Boric Acid
BORIC ACID
148
Items to compare
Conventional technology
Destruction technology Decomposition through pressure induced chemical decomposition as it suffers a high anisotropic compression
Efficiency
Amount of destruction
By Products Cubic HBO2, ice-VI, ice-VII
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High because of X-ray powder diffraction, infrared spectroscopy measurements
Running cost Low
Working Area Large
Number of Labor 1
Comments ”Pressure-Induced Chemical Decomposition and Structural Changes of Boric Acid”, Alexei Yu. Kuznetsov, Altair S. Pereira, Andrei
A. Shiryaev, Julien Haines, Leonid Dubrovinsky, Vladimir Dmitriev, Phil Pattison and Nicolas Guignot, J.Phys. Chem. B 2006, 110,
13858-13865, [100]
Table 87: Conventional technology to destroy Acetic Acid
ACETIC ACID
Items to compare
Conventional technology
Destruction technology
Photo catalytic decomposition (UV-Lamp) using fluidized reactor which increases contact between photo source and catalyst
Efficiency Over 70% can reach to 90% using Al/TiO2
Amount of destruction
By Products
Skilled Labor No
Dangerous process
No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost Moderate as major investment is UV lamp and fluidizer bed
Running cost High because of high temperature catalyst preparation
Working Area Small
Number of Labor 1
Comments Comparing photo catalytic decomposition over TiO2 and Al/TiO2, Al/TiO2 had higher removal rate than TiO2. It was because that Al metal increased acidic site and acidic site was used as active site. Calculated mass coefficient supported the
149
results
”Photo catalytic decomposition of gaseous acetic acid in fluidized reactor”, Y.H. Son, J.Y. Ban, S.C. Lee, M. Kang and S.J. choung,
[101]
Table 88: Conventional technology to destroy Acetic Acid
ACETIC ACID
Items to compare
Conventional technology
Destruction technology
Decomposition using UV light and thin films of TiO2 and TiO2/SiO2 prepared by the sol-gel method
Efficiency
Amount of destruction
By Products H2O, CO2
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High because of thermogravimeteric differential thermal analysis(TG-DTA), fourier transformation and infrared spectroscopy, specific area analysis (BET), X-ray diffraction (XRD), transmission electron microscopy (TEM), batch photo reactor
Running cost High because of high temperature for thin film preparation
Working Area Large
Number of Labor 1
Comments TiO2/SiO2 thin film having a pure-anatase phase showed a higher photo catalytic activity than did the pure-anatase SiO2
”Photo catalytic decomposition of Acetic Acid over TiO2 and TiO2/SiO2 thin films prepared by the sol-gel method”, Man Sig Lee,
Ju Dong Lee and Seong-Soo Hong, J.Ind. Eng. Chem. Vol.11, No.4, (2005) 495-501, [102]
Table 89: Conventional technology to destroy Acetic Acid
ACETIC ACID
Items to compare
Conventional technology
Destruction technology
Photo-catalytic oxidation (PCO) and decomposition (PCD) of acetic acid on TS-1 and Ti-MCM-4 1 catalysts
Efficiency
Amount of destruction
By Products CO2,CH4,C2H6 for P-25 TiO2,CO2 and CH4 on TS-1 and Ti-MCM-41
Skilled Labor Yes
Dangerous process
No
150
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost Yes because of spectrometer, XRD, UV-DRS
Running cost Low
Working Area Large
Number of Labor 1
Comments The rates of product formation during PCD were lower compared with PCO
”Photo catalytic Oxidation and Decomposition of Acetic acid over TiO2, TS-1 and Ti-MCM-41 Catalysts”, J.H Park, S.G. Kim, S.S.
Park, S.S. Hong and G.D Lee, Materials Science forum Vols. 510-511(2006) PP34-37, [103]
Table 90: Conventional technology to destroy Hydrogen Peroxide
HYDROGEN PEROXIDE
Items to compare
Conventional technology
Destruction technology Catalytic decomposition using Potassium Iodide
Efficiency
Amount of destruction
By Products O2, H2O
Skilled Labor No
Dangerous process Yes
Automatic No
PTOTMBD No
PTODABD No
Investment cost Low
Running cost Low
Working Area Small
Number of Labor 1
Comments It’s a very cheap process
”Catalytic decomposition of Hydrogen Peroxide by Iodide”, [104]
Table 91: Conventional technology to destroy Sulfuric Acid
SULFURIC ACID
Items to compare
Conventional technology
Destruction technology Catalytic thermal decomposition using catalysts Pd-Ag alloy and Fe2O3
Efficiency
Amount of destruction
By Products N2, H2SO4, SO3, SO2, O2, H2O
Skilled Labor Yes
Dangerous process Yes
Automatic Yes
PTOTMBD No
151
PTODABD Yes
Investment cost High
Running cost High
Working Area Small
Number of Labor 1
Comments
”Catalytic thermal decomposition of sulphuric acid in sulphur-iodine cycle for hydrogen production”, V.Barbarossa, S.Brutti,
M.Diamanti, S.Sau, G. De Maria, International Journal of Hydrogen Energy 31 (2006) 883-890, [105]
Table 92: Conventional technology to destroy Nitric Acid esters
NITRIC ACID ESTERS
Items to compare
Conventional technology
Destruction technology Thermal decomposition of explosive nitric acid esters in waste water effluents of the explosive industry
Efficiency
Amount of destruction
By Products
Skilled Labor
Dangerous process
Automatic
PTOTMBD
PTODABD
Investment cost
Running cost
Working Area
Number of Labor
Comments
”Process for the decomposition of explosive nitric acid esters dissolved in wastewaters”, Wilhelm Gresser, Klaus Schelhase, Heinz
Frisch, Klaus Kaschel, Berent Reinecke, Wilelm, H.Trautmann, United States Patent, Patent number 5,011,614, [106]
Table 93: Conventional technology to destroy Acetic Acid Monomer and Dimer
ACETIC ACID MONOMER AND DIMER
Items to compare
Conventional technology
Destruction technology Decomposition of acetic acid monomer and dimer on Ni(100) using temperature programmed reflection absorption infrared spectroscopy in concert with reflection absorption infrared spectroscopy
Efficiency
Amount of destruction
By Products CO2, H2
Skilled Labor Yes
Dangerous process No
Automatic Yes
152
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost High
Working Area Small
Number of Labor 1
Comments
”Acetic Acid Decomposition on Ni(100):Intermediate Adsorbate Structures by Reflection Infrared Spectroscopy”, Eric W. Scharpf
and Jay B. Benziger, The Journal of Physical Chemistry, Vol.91, No.22, 1987, [107]
Table 94: Conventional technology to destroy Sulfuric Acid
SULFURIC ACID
Items to compare
Conventional technology
Destruction technology Decomposition using gamma rays by the direct action of the radiation on the acid and for reactions of the acid with H and OH radicals produced by decomposition of water
Efficiency
Amount of destruction
By Products SO2
Skilled Labor
Dangerous process Yes
Automatic
PTOTMBD Yes
PTODABD No
Investment cost
Running cost
Working Area
Number of Labor
Comments SO2 was produced at a rate which increased with increasing acid concentration and decreased with increasing dose
”The Decomposition of Sulfuric Acid by cobalt gamma rays”, C.J. Hochanadel, J.A.Ghormley and t.J. Sworski, [108]
Table 95: Conventional technology to destroy Acetic Acid
ACETIC ACID
Items to compare
Conventional technology
Destruction technology Decomposition of acetic acid using a non-degradable organic compound, with in 120 mins of UV radiation under the initial concentration of 500 ppm. Hydrogen per oxide is used for oxidation
Efficiency 100%
Amount of destruction 500 ppm solution for 120 mins MUST BE L/min
By Products
153
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost Moderate
Running cost Low
Working Area Small
Number of Labor 1
Comments Acetic acid was completely decomposed within 120 mins of UV radiation under the initial concentration of 500 ppm. Acetic acid was efficiently decomposed with TiO2-UV-H2O2, Fe-H2O2-UV and UV-H2O2 except TiO2-UV system. UV-H2O2 reaction was the most efficient oxidation method
”Decomposition of acetic acid by advanced oxidation processes”, Ju Young Park and In Hwa Lee”, Korean J.Chem.Eng. 26(2),
387-391(2009), [109]
Table 96: Conventional technology to destroy Hydrogen Iodide
HYDROGEN IODIDE
Items to compare
Conventional technology
Destruction technology Decomposition of hydrogen iodide at constant temperature
Efficiency 11.26%
Amount of destruction
By Products Iodine, HI
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD Yes
PTODABD No
Investment cost Moderate as the entire apparatus was made of pyrex
Running cost High as it’s a high temperature process
Working Area Small
Number of Labor 1
Comments
”The decomposition of Hydrogen Iodide”, H.Austin Taylor, J.Phys.Chem, 1928, 28(9), pp984-991, DOI: 10.1021/j150243a007,
[110]
Table 97: Conventional technology to destroy Citric Acid
CITRIC ACID
Items to compare
Conventional technology
Destruction technology Decomposition of citric acid using sulfuric acid as catalyst
Efficiency 92-97%
154
Amount of destruction
By Products CO, H2O, acetone, dicarboxylic acid
Skilled Labor No
Dangerous process No
Automatic No
PTOTMBD Yes
PTODABD Yes
Investment cost Low
Running cost Low
Working Area Small
Number of Labor 1
Comments
”The decomposition of citric acid by sulfuric acid”, Edwin O.Wiig, [111]
Table 98: Conventional technology to destroy Benzoic Acid
BENZOIC ACID
Items to compare
Conventional technology
Destruction technology Thermal decomposition of benzoic acid and its derivatives containing (OH) and (NH2) , (COOH) and (SO3H) to define the influence of chemical structure on their thermal decomposition
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process
Automatic
PTOTMBD
PTODABD
Investment cost High as DTA, TG and DTG are the requirement
Running cost Low
Working Area Large feasible for lab scale
Number of Labor 1
Comments
”Studies on the thermal decomposition of benzoic acid and its derivatives”, M.Wesolowski and T.Konarski, Journal of Thermal
Analysis and Calorimetry Vol.55 (1999) 995-1002, [112]
Table 99: Conventional technology to destroy Formic Acid
FORMIC ACID
Items to compare
Conventional technology
Destruction technology The thermal decomposition of formic acid (HCOOH) adsorbed on Pd(100) surface
Efficiency
155
Amount of destruction
By Products CO, CO2, H2
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD
PTODABD
Investment cost High
Running cost High
Working Area Large feasible for lab scale
Number of Labor 1
Comments
”The decomposition of formic acid on Pd (100)”, D.Sander and W.Erley, J.Vac.Sci. Technol. A8(4), Jul/Aug 1990, [113]
Table 100: Conventional technology to destroy Formic Acid
FORMIC ACID
Items to compare
Conventional technology
Destruction technology The adsorption and decomposition of formic acid (HCOOH) on Ni (111) surface
Efficiency
Amount of destruction
By Products CO2, H2, CO
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost High
Working Area Large
Number of Labor 1
Comments
”The adsorption and decomposition of formic acid on Ni (111): The identification of formic anhydride by vibrational
spectroscopy”, W.Erley and D.Sander, J.Vac.Sci.Technol. A7 (3), May/Jun 1989, [114]
Table 101: Conventional technology to destroy Benzoic Acid
BENZOIC ACID
Items to compare
Conventional technology
Destruction technology Anaerobic decomposition of Benzoic acid during methane fermentation. II. Fate of Carbons one and seven
Efficiency
Amount of destruction
156
By Products CO2, CH4
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD Yes
PTODABD Yes
Investment cost
Running cost Low
Working Area
Number of Labor More than 1
Comments
”The Anaerobic Decomposition of Benzoic Acid During Methane Fermentation.II. Fate of Carbons One and Seven”, L.R.Fina and
A:M.Fiskin, Archives of Biochemistry and Biophysics 91, 163-165, [115]
Table 102: Conventional technology to destroy Benzoic Acid
BENZOIC ACID
Items to compare
Conventional technology
Destruction technology Anaerobic decomposition of benzoic acid during methane fermentation IV. Dearomatization of the ring and volatile fatty acid formed on ring rupture
Efficiency
Amount of destruction
By Products CO2, CH4
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD Yes
PTODABD Yes
Investment cost High
Running cost Low
Working Area
Number of Labor More than 1
Comments
”The Anaerobic Decomposition of Benzoici Acid during Methane Fermentation IV.Dearomatization of the Ring andn Volatile
Fatty acid Formed on Ring Rupture”, C.L.Keith, R.L.Bridges, L.R.Fina,K.L.Iverson, J.A.Cloran, Archives of Microbiology 118, 173-
176, [116]
Table 103: Conventional technology to destroy Hydrogen Iodide
HYDROGEN IODIDE
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of HI for IS thermo chemical cycle were performed at high temperatures (300-500 °C) using three kinds of
157
catalysts ; Pt/activated carbon, Pt/Alumina and only activated carbon
Efficiency
Amount of destruction
By Products Hydrogen
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD Yes
Investment cost High because of SEM, XRD, EDAX, BET analysis, gas chromatographer
Running cost High
Working Area Large
Number of Labor 1
Comments HI conversion of all the tested catalysts increased with the increasing decomposition temperature and the HI conversion of platinum supported catalysts was higher than that of only activated carbon
”The catalytic decomposition of hydrogen iodide in the IS thermochemical cycle”, Chu-Sik Park, Jung-Min KIM, Kyoung-Soo Kang,
Gab-Jin Hwang, Ki-Kwang Bae,WHEC 16/13-16 June 2006-Lyon France, [117]
Table 104: Conventional technology to destroy Yeast Nucleic Acid
YEAST NUCLEIC ACID
Items to compare
Conventional technology
Destruction technology The decomposition of yeast nucleic acid by a heat-resistant enzyme
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic
PTOTMBD Yes
PTODABD Yes
Investment cost
Running cost
Working Area
Number of Labor 1
Comments
”The decomposition of yeast nucleic acid by a heat-resistant enzyme”, Rene J. Dubos and R.H.S Thompson, The Journal of
Biological Chemistry, [118]
Table 105: Conventional technology to destroy Nitric Acid
NITRIC ACID
Items to compare
Conventional technology
158
Destruction technology Thermal decomposition of nitric acid vapor in two glass cells of considerably different surface-to-volume ration from 100 to 465 °C
Efficiency
Amount of destruction
By Products NO2, water and oxygen
Skilled Labor Yes
Dangerous process Yes
Automatic No
PTOTMBD Yes
PTODABD No
Investment cost Moderate
Running cost High
Working Area Lab Scale
Number of Labor 1
Comments
”The Kinetics of the Thermal Decomposition of Nitric Acid Vapor”, Harold S. Johnston, Louise Foering, Yu-sheng Tao and G.H.
Messerly, J.Am.Chem.Soc, 1951, 73(5), pp2319-2321, DOI: 10.1021/ja01149a120, [119]
Table 106: Conventional technology to destroy Hydrogen Bromide
HYDROGEN BROMOIDE
Items to compare
Conventional technology
Destruction technology The radiochemical formation of HBr and then it’s decomposition using ion pair yield for a stoichiometric mixture
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process Yes
Automatic No
PTOTMBD Yes
PTODABD Yes
Investment cost High
Running cost High
Working Area
Number of Labor 1
Comments
”The Radiochemical synthesis and decomposition of Hydrogen Bromide”, S.C.Lind and Robert Livingston, [120]
Table 107: Conventional technology to destroy Acetic Acid
ACETIC ACID
Items to compare
Conventional technology
159
Destruction technology Decomposition of acetic acid by making use of reliable molecular orbital methods
Efficiency
Amount of destruction
By Products
Skilled Labor
Dangerous process
Automatic
PTOTMBD
PTODABD
Investment cost
Running cost
Working Area
Number of Labor
Comments Ab Initio MO Calculations were used
”Theoretical Study of the Thermal Decomposition of Acetic Acid: Decarboxylation Versus Dehydration”, Minh Tho Nguyen,
Debasis Sengupta, Grett Raspoet, Luc G. Vanquickenborne, J.Phys.Chem.1995,99,11883-11888, [121]
Table 108: Conventional technology to destroy Aqueous Chromic Acid
AQUEOUS CHROMIC ACID
Items to compare
Conventional technology
Destruction technology Decomposition of aqueous chromic acid solutions in sulfuric acid solutions
Efficiency
Amount of destruction
By Products Chromium dioxide, HCrO2
Skilled Labor Yes
Dangerous process Yes
Automatic Yes
PTOTMBD Yes
PTODABD No but the vessel should be well prepared
Investment cost High because of X-ray diffraction
Running cost Moderate as the thermal decomposition temperature is 300-324 °C
Working Area
Number of Labor 1
Comments
”The Thermal Decomposition of Aqueous Chromic Acid and Some Properties of the Resulting Solid Phases”, B.J.Thamer,
R.M.Douglass, E. Starizky, J.Am.Chem.Soc, 1957, 79(3), pp. 547-550, DOI: 10.1021/ja01560a013, [122]
Table 109: Conventional technology to destroy Hydrogen Chloride
HYDROGEN CHLORIDE
Items to compare
Conventional technology
160
Destruction technology Thermal decomposition of HCl measured by ARAS and IR diode Laser Spectroscopy. ARAS stands for Atomic resonance absorption spectroscopy measurements
Efficiency
Amount of destruction
By Products Hydrogen
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High because of atomic resonance absorption spectroscopy and infrared diode laser
Running cost Very high as the operating temperature is 2500-4600 K
Working Area Lab Scale
Number of Labor 1
Comments
”Thermal Decomposition of HCl Measured by ARAS and IR Diode Laser Spectroscopy”, G.N.Schading and P.Roth, Combustion and
Flame 99:467-474(1994), [123]
Table 110: Conventional technology to destroy Formic Acid
FORMIC ACID
Items to compare
Conventional technology
Destruction technology
Photo catalytic decomposition of formic acid under visible light irradiation over V-ion implanted TiO2 thin film photo catalysts prepared on quartz substrate by ionized cluster beam (ICB) deposition method
Efficiency 100%
Amount of destruction
By Products CO2, H2O
Skilled Labor Yes
Dangerous process
No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost Very High
Running cost High
Working Area Large
Number of Labor 1
Comments
”Photo catalytic decomposition of formic acid under visible light irradiation over V-ion implanted TiO2 thin film photo catalysts
prepared on quartz substrate by ionized cluster beam (ICB) deposition method”, Jinkai Zhou, Masato Takeuchi, X.S.Zhao, Ajay
K.Ray, Masakazu Anpo, Catalysis Letters Vol.106, Nos.1-2, January 2006, DOI: 10.1007/s10562-005-9192-5, [124]
161
3.2. Bases
Table 111: Conventional technology to destroy Sodium Bi Carbonate
SODIUM BI CARBONATE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of NaHCO3 under different atmospheres (dry nitrogen, air and CO2) with various heating rates
Efficiency
Amount of destruction
By Products CO2, H2O
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High because of TGA, DTG and milling cost
Running cost Low
Working Area Large
Number of Labor 1
Comments With the reduction in the particle size of sodium bicarbonate, the decomposition reaction was accelerated
”A method of assessing solid state reactivity illustrated by thermal decomposition experiments on sodium bicarbonate”, Pavan
K.Heda, David Dollimore, Kenneth S. Alexander, Dun chen, Emmeline Lae, Paul Bicknell, Thermochimica Acta 255(1995) 255-272,
[125]
Table 112: Conventional technology to destroy Sodium Carbonate
SODIUM CARBONATE
Items to compare
Conventional technology
Destruction technology Decomposition of Na2CO3 in temperature range of 25-1040 °C using different crucible materials and atmospheres
Efficiency
Amount of destruction
By Products
Skilled Labor No
Dangerous process
Automatic
PTOTMBD Yes
PTODABD Yes
Investment cost Moderate
Running cost High as the decomposition doesn’t occur below 800 °C
162
Working Area
Number of Labor 1
Comments
”Drying and decomposition of Sodium Carbonate”, Arthur E. Newkirk and Ifigenia Aliferis, Analytical Chemistry Vol.30, No.5 May
1958, [126]
Table 113: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Thermal adsorption and decomposition of NH3 on Ni(110) surface by means of thermal desorption and high resolution electron energy loss (HREEL) spectroscopy in the temperature range of 110-500 K
Efficiency
Amount of destruction
By Products NH+H
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High because of UHV chamber, LEED, AES, quadrupole mass spectrometer, rotatable single pass high resolution electron energy loss spectrometer
Running cost High
Working Area Large
Number of Labor 1
Comments
”Adsorption and thermal decomposition of ammonia on a Ni (110) surface: isolation and identification of adsorbed NH2 and
NH”, I.C.Bassignana, K.Wagemann J. Juppers and G.Ertl, Surface Science 175(1986) 22-44 North Holland, Amsterdam, [127]
Table 114: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Ammonia adsorption and decomposition on a Ni(110) surface
Efficiency
Amount of destruction
By Products Surface nitrides are formed
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
163
PTODABD Yes
Investment cost High
Running cost High
Working Area
Number of Labor 1
Comments Decomposition reaction of NH3 on Ni(110) resembles the pattern and efficiency found on an iron (110) single crystal
”Ammonia adsorption and decomposition on a Ni (110) surface”, M.Grunze, M. Golze, R.K.Driscoll, P.A. Dowben,
J.Vac.Sci.Technol.18 (2), March 1981, [128]
Table 115: Conventional technology to destroy Barium Hydroxide
BARIUM HYDROXIDE
Items to compare
Conventional technology
Destruction technology Thermal decomposition
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process
Automatic
PTOTMBD Yes
PTODABD No
Investment cost High because of DAT, TG, DTG, high temperature X-ray diffractometer, high temperature Raman Scattering
Running cost Low
Working Area Large
Number of Labor 1
Comments
”Hydrates of Barium Hydroxide. Preparation, thermal decomposition and X-ray data”, H.D.Lutz, W.Eckers, H.Christan and
B.Engelen, Thermochimica Acta, 44(1981) 337-343, [129]
Table 116: Conventional technology to destroy Potassium Hydroxide
POTASSIUM HYDROXIDE
Items to compare
Conventional technology
Destruction technology Formation of KOH on Ag(111) and its conversion to carbonate studies through x-ray photo electron spectroscopy , ultraviolet photo electron spectroscopy, temperature programmed desorption
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
164
Dangerous process No
Automatic No
PTOTMBD No
PTODABD No
Investment cost High
Running cost Low
Working Area Large
Number of Labor 1
Comments Carbonate formation from KOH and CO2 is facile at 300 K but not at 100 K. K2CO3 is stable at 800 K and thermally decomposes to CO2, O2 and K
”Carbonate formation and decomposition on KOH/Ag(111) P.M. Blass, X.L. Zhou and J.M. White, J.VAC.Sci.Technol.A 7(3),
May/Jun 1989, [130]
Table 117: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of NH3 to produce hydrogen using different catalysts
Efficiency 99%
Amount of destruction
By Products Hydrogen, Nitrogen
Skilled Labor
Dangerous process
Automatic
PTOTMBD
PTODABD Yes
Investment cost
Running cost
Working Area
Number of Labor
Comments The absence of any undesirable by-products makes this process an ideal source of hydrogen for fuel cells
”Catalytic ammonia decomposition: Cox-free hydrogen production for fuel cell applications”, T.V.Choudhary, C. Sivadinarayana
and D.W.Goodman, Catalysis Letters Vol.72, No.3-4, 2001, [131]
Table 118: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of NH3 at low temperature in micro-fabricated reactors using ruthenium catalysts promoted with barium
Efficiency
165
Amount of destruction
By Products
Skilled Labor
Dangerous process
Automatic
PTOTMBD
PTODABD Yes
Investment cost
Running cost
Working Area
Number of Labor
Comments
”Catalytic ammonia decomposition: miniaturized production of Cox-free hydrogen for fuel cells”, Rasmus Zink Sorensen, Laerke
J.E. Nieslsen, Soren Jense, Ole Hansen, tue Johannessen, Ulrich Quaade, Claus Hvidd Christensen, Catalysis Communications 6
(2005) 229-232, [132]
Table 119: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Decomposition of NH3 with Ru catalysts using fly ash, whose enhanced surface area improves dispersion of Ru particles, resulting in higher catalytic activity
Efficiency 94.60%
Amount of destruction
By Products Hydrogen
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High because of gas chromatographer, vertical fixed bed flow reactor, X-ray diffractometer, adsorption analyzer, X-ray photoelectron spectroscopy
Running cost Moderate
Working Area Large
Number of Labor 1
Comments
”Catalytic decomposition of ammonia over fly ash supported Ru catalysts”, Li, Shaobin Wang, Zhonghua Zhu, Xiangdong Yao,
Zifeng Yan, Fuel Processing Technology 89(2008) 1106-1112, [133]
Table 120: Conventional technology to destroy Ammonia
AMMONIA
166
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of NH3 using a cracking-cell filled with Al2O3 fiber using a quadrupole mass spectrometer
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost Moderate because of ultrahigh vacuum chamber, cracking cell, quadrupole mass spectrometer
Running cost Moderate
Working Area Large scale/Small
Number of Labor 1
Comments NH3 decomposition rate increased with the increase of the cracking cell temperature until 500 °C and decreased above 500 °C
”Catalytic decomposition of ammonia gas using aluminum oxide for GaN formation”, Seikoh Yoshida and Masahiro Sasaki,
Journal of Crystal Growth 135 (1994) 633-35, [134]
Table 121: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of NH3 on heated W and Ru-coated W wires
Efficiency
Amount of destruction
By Products NH2, H
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High because of mass flow controller, cylindrical stainless steel reaction chamber, X-ray photo electron spectroscopy, YAG pumped dye laser, solar blind photomultiplier, oscilloscope, mass spectrometer
Running cost Low
Working Area Large
Number of Labor 1
Comments Decomposition efficiency of both the wires was the same
167
Catalytic decomposition of NH3 on heated Ru and W surfaces”, Hironobu Umemoto, Yuta Kashiwagi, Kesiuke Ohdaira, Hiroyuki
Kobayashi, Kanji Yasui, TSF-28821; doi:10.1016/j.tsf.2011.01.289, [135]
Table 122: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of Ammonia over Nitrided MoNx/alpha-Al2O3 and NiMoNy/alpha-Al2O3 catalysts
Efficiency 98 – 99 %
Amount of destruction
By Products NH3
Skilled Labor Yes
Dangerous process
Automatic
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost Moderate
Working Area Lab Scale
Number of Labor 1
Comments In this paper, it is found that the nitride catalysts are very active for NH3 decomposition and the conversion can be as high as 99.8% even at 650 °C which is far below the temp of commercial process
”Catalytic decomposition of Ammonia over Nitrided MoNx/alpha-Al2O3 and NiMoNy/alpha-Al2O3 catalysts”, Changhai Linag,
Wenzhen Li, Zhaobin Wei,Qin Xin and Can Li, Ind.Eng.Chem.Res.2000,39,3694-3697, [136]
Table 123: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of NH3 to nitrogen by selective oxidation over a bimetallic CuO/CeO2 nanoparticle catalyst at temp b/w 423-673 K
Efficiency 98%
Amount of destruction
By Products NO, N2
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High because of SEM/EDS, BET surface are analyzer, ATR-FTIR
168
spectrometer, PSA, TEM
Running cost Low
Working Area Large but lab scale
Number of Labor 1
Comments The processes involving catalysts for the decomposition are expensive mostly because of the cost required for catalyst preparation
”Catalytic decomposition of Ammonia over Bimetallic CuO/CeO2 Nanoparticle Catalyst”, Chang-Mao Hung, Hung, Aerosol and
Air Quality Research, Vol.8, No.4, pp.447-458, [137]
Table 124: Conventional technology to destroy Aluminum Hydroxide and Magnesium Hydroxide
ALUMINUIM HYDROXIDE AND MAGNESIUM HYDROXIDE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of Al(OH)3 and Mg(OH)2 to form Alumina and Magnesia at high tempt 973-1123 K
Efficiency More than 95%
Amount of destruction
By Products
Skilled Labor No but just for the analytical instruments
Dangerous process No
Automatic N/A
PTOTMBD Yes
PTODABD No
Investment cost High but only x-ray diffractometer, Lindberg box furnace and thermogravimeteric analyzer were used
Running cost High
Working Area Large
Number of Labor 1
Comments
”Chemical Kinetics and Reaction Mechanism of Thermal Decomposition of Aluminum Hydroxide and Magnesium Hydroxide at
High Temperatures (973-1123)”, Lenwhei chen, Shuh-Kwei Hwang, Shyan Chen, Ind.Eng.Chem.Res.1989,28,738-742, [138]
Table 125: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Decomposition of NH3 to N2 over limestone to reduce NOx emission from fluidized bed combustors and effect of CO2 and H2O on product of NH3 decomposition over limestone
Efficiency
Amount of destruction
By Products NO, N2, N2O
Skilled Labor
169
Dangerous process
Automatic
PTOTMBD No
PTODABD No
Investment cost
Running cost High as it’s a high temperature process
Working Area
Number of Labor
Comments From NH2-CO2 mixture (NH2)2CO was formed though NH3 decomposition over both calcined and uncalcined limestone but from NH2-CO2-H2O mixture (NH2)2CO was not formed
”Decomposition of NH3 over calcined and uncalcined limestone under fluidized bed combustion conditions”, Tadaaki Shimizu,
Eisuke Karahashi, Takuya Yamaguchi, Makoto Inagaki, Energy and Fuels 1995, 9, 962-965, [139]
Table 126: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Solid-catalyzed decomposition reaction of NH3 over quartz sand at 840-960 °C
Efficiency
Amount of destruction
By Products NH3, N2, H2, H2O
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost Moderate as the main investment costs are mass spectrometer and fluidized bed reactor
Running cost Moderate, not low as it’s a high temperature process
Working Area Small
Number of Labor 1
Comments Fluidized bed technology is an economic and efficient method of burning a verity of fuels with low SO2 and NOx emissions
”Decomposition of NH3 over Quartz Sand at 840-960C”, D.A.Cooper and E.B. Ljungstrom, Energy and Fuels, Vol.2, No.5, 1988,
[140]
Table 127: Conventional technology to destroy Sodium Bi Carbonate
SODIUM BI CARBONATE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of NaHCO3 in a closed system
170
Efficiency
Amount of destruction
By Products Na2CO3, CO2, H2O
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost Low
Working Area Lab Scale
Number of Labor 1
Comments
”Differential thermal analysis of the decomposition of sodium bicarbonate and its simple double salts”, Edward M.Barrall,
L.B.Rogers, J.Inorg.Nucl.Chem, 1966, Vol.28, pp.41 to 51, [141]
Table 128: Conventional technology to destroy Sodium Hydride
SODIUM HYDRIDE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of sodium hydride (500 K-800 K)
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High
Running cost Low
Working Area Lab Scale
Number of Labor 1
Comments
”DTA study of the kinetics of sodium hydride decomposition”,Jsubrt and K.tobola, Journal of Thermal Analysis Vol.10 (1976) 5-
12, [142]
Table 129: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Electrolytic decomposition characteristics of ammonia to nitrogen at IrO2 anode
Efficiency
171
Amount of destruction
By Products N2
Skilled Labor
Dangerous process
Automatic
PTOTMBD
PTODABD
Investment cost High
Running cost Low
Working Area
Number of Labor 1
Comments
”Electrolytic decomposition characteristics of ammonia to nitrogen at IrO2 anode”, Kwang-Wook Kim, Young-Jun Kim, In-Tae
Kim, Geun-II Park, Eil Hee Lee, [143]
Table 130: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Electrolytic decomposition of ammonia to nitrogen
Efficiency 100%
Amount of destruction
By Products Nitrogen
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD Yes
Investment cost Moderate
Running cost Low
Working Area Lab scale/small
Number of Labor 1
Comments The electrolytic decomposition efficiency of ammonia is affected by the PH change of ammonia solution
”Electrolytic decomposition of ammonia to nitrogen in a multi-cell-stacked electrolyzer with a self-pH-adjustment function”,
Kwang-Wook Kim, In-Tae Kim Geun-IL Park, Eil Hee Lee, Journal of Applied Electrochemistry (2006) 36: 1415-1426 DOI:
10.1007/s10800-006-92348, [144]
Table 131: Conventional technology to destroy Magnesium Hydroxide
MAGNESIUM HYDROXIDE
Items to compare
Conventional technology
Destruction technology Thermal decomposition at 300-600 °C
172
Efficiency
Amount of destruction
By Products Water, hydrogen, oxygen
Skilled Labor No
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost High as it’s a high temperature process 1000 °C
Working Area Large
Number of Labor 1
Comments
”Hydrogen Release during the Thermal Decomposition of Magnesium Hydroxide to Magnesium Oxide”, R.Martens, H.Gentsch
and F.Freund, Journal of Catalysis 44, 366-372 (1976), [145]
Table 132: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Photo decomposition of NH3 using Pt-TiO2 as a photo catalyst
Efficiency 21.60%
Amount of destruction
By Products H2, N2
Skilled Labor Yes
Dangerous process
Automatic
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost Low
Working Area Lab Scale
Number of Labor 1
Comments
”Photodecomposition of ammonia to dinitrogen and dihydrogen on platinized TiO2 nanoparticles in an aqueous solution”,
Junichi Nemoto, Norihiko Gokan, Hirohito Ueno, Masao Kaneko, Journal of Photochemistry and Photobiology A: Chemistry
185(2007) 295-300, [146]
Table 133: Conventional technology to destroy Magnesium Hydroxide
MAGNESIUM HYDROXIDE
Items to compare
Conventional technology
Destruction technology The decomposition of Mg(OH)2 in an electron microscope
Efficiency
173
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost No
Working Area Large but lab scale
Number of Labor 1
Comments
”The Decomposition of Magnesium Hydroxide in an Electron Microscope”, J.F.Goodman, Proceeding of the Royal Society of
London. Series A, Mathematical and Physical Sciences, Vol.247, No.1250 (Sep.30, 1958), pp.346-352, [147]
Table 134: Conventional technology to destroy Sodium Carbonate
SODIUM CARBONATE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of Na2CO3 by effusion method
Efficiency
Amount of destruction
By Products CO2
Skilled Labor Yes
Dangerous process Yes
Automatic No
PTOTMBD
PTODABD
Investment cost High
Running cost High as it’s a high temperature process
Working Area
Number of Labor
Comments The experiment conducted were not accurate
”The thermal decomposition of sodium carbonate by the effusion method” Ketil Motzfeldt, J.Phys.Chem, 1955, 59(2), pp. 139-
147, DOI: 10.1021/j150524a0II, [148]
Table 135: Conventional technology to destroy Lithium Hydroxide
LITHIUM HYDROXIDE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of LiOH at 500-1300 K
Efficiency
Amount of destruction
By Products
174
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High because of laser induced fluorescence method and quadrupolemass spectrometery, TG, DTA
Running cost High because of its high temperature 500-1300 K
Working Area Lab Scale
Number of Labor 1
Comments
”Gas-Phase Hydroxyl Radical Emission in the Thermal Decomposition of Lithium Hydroxide”, Suguru Noda, Masateru Nishioka
Masayoshi Sadakata, J.Phys.Chem.B 1999, 103, 1954-1959, [149]
Table 136: Conventional technology to destroy Calcium Hydroxide
CALCIUM HYDROXIDE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of Ca(OH)2 by depositing Ca(OH)2 particles on substrate
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes as the solution is made
PTODABD No
Investment cost High because of DSC, DTA, X-ray diffractometer, SEM
Running cost Low
Working Area Large
Number of Labor 1
Comments
”Thermal decomposition of calcium hydroxide deposited on the substrate”, Y.Sawada, Y.Ito, Thermochimica Acta, 232(1994) 47-
54, [150]
Table 137: Conventional technology to destroy Strontium Hydroxide
STRONTIUM HYDROXIDE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of Sr(OH)2
Efficiency
Amount of destruction
By Products H2O
175
Skilled Labor Yes
Dangerous process Yes as it is done in open air
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High because of X-ray diffraction Spectroscopy
Running cost High as it’s a high temperature process (700 °C)
Working Area Lab scale large
Number of Labor 1 Comments
”Thermal decomposition of strontium hydroxide”, R.Dinescu and M.Preda, Journal of Thermal Analysis, Vo.5 (1973) 465-473,
[151]
Table 138: Conventional technology to destroy Sodium Hydroxide
SODIUM HYDROXIDE
Items to compare
Conventional technology
Destruction technology Thermal dissociation of NaOH upon evacuation at varied temperatures
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost
Running cost High as it’s a high temperature process 750-1023 K
Working Area
Number of Labor 1
Comments
”Thermal dissociation of Sodium Hydroxide upon Evacuation”, V.P.Yurkiniskii, E.G.Firsova, S.A.Proskura, Russian Journal of
Applied Chemistry, Vol. 78 No.3 2005, pp.360-362, [152]
Table 139: Conventional technology to destroy Barium Hydroxide
BARIUM HYDROXIDE
Items to compare
Conventional technology
Destruction technology Thermal decomposition at 400-600 °C
Efficiency
Amount of destruction
By Products BaO
Skilled Labor Yes specially because of analytical instruments
176
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High because of DTA, X-ray diffraction, TGA
Running cost High because of high temp
Working Area Large
Number of Labor 1
Comments
”Thermal decomposition of the hydrates of Barium Hydroxide”, G.M.Habashy and G.A. Kolta, J.Inorg, Nucl.Chem, 1972, Vol.34,
pp. 57-67, [153]
Table 140: Conventional technology to destroy Sodium Bi Carbonate
SODIUM BI CARBONATE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of NaHCO3 by DTA
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High but not as other as only DTA is required
Running cost
Working Area Lab Scale Small
Number of Labor 1
Comments The decomposition of sodium bicarbonate was studied at different particle sizes and different heating rates
”Thermal decomposition kinetics of sodium bicarbonate by differential thermal analysis”, K.S. Subramanian, T.P. Radhakrishnan
and A.K. Sundaram, Journal of Thermal Analysis, Vol.4 (1972), 89-93, [154]
Table 141: Conventional technology to destroy Nickel Hydroxide
NICKLE HYDROXIDE
Items to compare
Conventional technology
Destruction technology Thermal decomposition mechanism of Ni(OH)2 determined using X-ray diffraction and thermal analysis
Efficiency
Amount of destruction
By Products H2O
Skilled Labor Yes
177
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High because of X-ray diffraction and thermogravimeteric analysis
Running cost High because of high temp
Working Area Large
Number of Labor 1
Comments
”X-ray Diffraction Studies on the thermal decomposition Mechanism of Nickel Hydroxide”, Thimmasandra Narayan Ramesh,
J.Physc.Chem.B 2009, 113, 13014-13017, [155]
Table 142: Conventional technology to destroy Sodium Carbonate
SODIUM CARBONATE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of Na2CO3
Efficiency
Amount of destruction
By Products NaOH, CO2
Skilled Labor Yes
Dangerous process No but it can become because of autoclave
Automatic Yes
PTOTMBD Yes as the solution is made
PTODABD No
Investment cost Moderate
Running cost Moderate
Working Area Large but associated with the size of autoclave
Number of Labor 1
Comments Conversion rate decreased as sodium carbonate concentration decreased at the same steaming rate and temperature
”Thermal decomposition of sodium carbonate solutions”, Authur M.Thomas.Jr., J.Chem.Eng.Data, 1963, 8(1), pp51-54, DOI:
10.1021/je60016a014, [156]
Table 143: Conventional technology to destroy Calcium Carbonate
CALCIUM CARBONATE
Items to compare
Conventional technology
Destruction technology Thermal decomposition of CaCO3 using analytical and instrumental techniques to produce CaO
Efficiency
Amount of destruction
By Products CaO, CO2
178
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High because of TGA, MS, XRD, SEM
Running cost High
Working Area Large
Number of Labor 1
Comments
”Thermal Decomposition and Solid Characterization of Calcium Oxide in Limestone Calcination”, B.D. soares, C.E.Hori, C.E.A
Batista, H.M.Henriuqe, Materials Science Forum vols. 591-593 (2008) pp. 352-357, doi:
10.4028/22.scientific.net/MSF.591.593.352, [157]
Table 144: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology The decomposition of ammonia with wavelength of 2025-2140 Angstrom
Efficiency
Amount of destruction
By Products N2 (4%), H2 (96%)
Skilled Labor Yes
Dangerous process No as long as the safety measures are ensured
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High
Running cost Low
Working Area Lab Scale
Number of Labor 1
Comments
”The Photochemical decomposition of Ammonia”, Edwin O.Wiig, G.B.Kistiakowsky, J.Am.Chem.Soc, 1932, 54(5), pp. 1806-1820,
DOI: 10.1021/ja01344a012, [158]
Table 145: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology The mercury photosensitized decomposition of NH3 and NH3-propane mixtures
Efficiency
Amount of destruction
179
By Products H2, N2, CH4
Skilled Labor
Dangerous process
Automatic
PTOTMBD
PTODABD
Investment cost Moderate
Running cost Low
Working Area Lab Scale/Small
Number of Labor 1
Comments
”The Mercury Photosensitized decomposition of ammonia and ammonia-propane mixtures”, S.Takamuku and R.A.Back,
Canadian Journal of Chemistry, Volume 42(1964), [159]
Table 146: Conventional technology to destroy Ammonia
AMMONIA
Items to compare
Conventional technology
Destruction technology Thermal decomposition of NH3 using Mo as catalyst
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process Yes
Automatic No
PTOTMBD Yes
PTODABD No
Investment cost Moderate
Running cost High as 1097-1228 K is operating temperature
Working Area Small
Number of Labor More than 1
Comments
”The thermal decomposition of ammonia upon the surface of a molybdenum wire”, Robert E.Burk, Proc Natl Acad Sci USA 1972
February, 13 (2): 67-74, [160]
3.3. Organic Solvents
Table 147: Conventional technology to destroy Acetic Acid Monomer and DIMER
ACETIC ACID MONOMER and DIMER
Items to compare
Conventional technology
Destruction technology Decomposition of acetic acid monomer and dimer on Ni(100)
180
using temperature programmed reflection absorption infrared spectroscopy
Efficiency
Amount of destruction
By Products CO, CO2, H2, C(ad), O(ad)
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes
PTODABD No
Investment cost High because of temperature programmed reactor (TPR), mass analyzer, TPRAIS, RAIS, Auger electron spectroscopy
Running cost High as it involves high temperatures
Working Area Lab Scale Large
Number of Labor 1
Comments ”Acetic Acid Decomposition on Ni (100): Intermediate Adsorbate Structures by Reflection Infrared Spectroscopy”, Eric W. Scharpf
and Jay B. Benziger, J.Phys. Chem, 1987, 91(22), pp. 5531-5534 DOI: 10.1021/j100306a005, [161]
Table 148: Conventional technology to destroy CH3OH
CH3OH
Items to compare
Conventional technology
Destruction technology Adsorption and thermal decomposition of CH3OH on clean polycrystalline Al
Efficiency
Amount of destruction
By Products CH4, CO, CO2, H2
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes as Al was heated upto 900 K as well as cleaning
Investment cost High because of electron spectrometer, UPS, XPS, He resonance lamp, quadrupole mass spectrometer
Running cost Moderate
Working Area Lab Scale Large
Number of Labor 1
Comments Decomposition starts after 630 K
”Adsorption and decomposition of methanol on aluminium”, J.W.Rogers, Jr. and J.M. White, J.Vac.Sci. Technol, Vol.16, No.2.
Mar/Apr.1979, [162]
Table 149: Conventional technology to destroy Primary Alcohols and 1-Propanol
PRIMARY ALCOHOLS and 1-PROPANOL
181
Items to compare
Conventional technology
Destruction technology Adsorption and thermal decomposition of 1-Propanol and other primary alcohols on the Si(100) surface
Efficiency
Amount of destruction
By Products Aldehydes
Skilled Labor Yes
Dangerous process No but it can become if high vacuum chamber is not operated properly
Automatic Yes
PTOTMBD Yes
PTODABD Yes
Investment cost High due to AES, TDA, Ultra high vacuum chamber (UHV), quadrupole mass spectrometer
Running cost High
Working Area Lab Scale Large
Number of Labor 1
Comments
”Adsorption and thermal decomposition Chemistry of 1-Propanol and other primary alcohols on the Si (100) Surface”, Linhu
Zhang, April J. Carman, Sean M. Casey, J.Physc. Chem. B2003, 107, 8424-8432, [163]
Table 150: Conventional technology to destroy Triethylamine Alane
TRIETHYLAMINE ALANE
Items to compare
Conventional technology
Destruction technology Triethylamine alane decomposes on Al(111) single crystal surface at temperatures above 310 K
Efficiency
Amount of destruction
By Products Hydrogen, Triethylamine
Skilled Labor
Dangerous process
Automatic
PTOTMBD Yes
PTODABD Yes
Investment cost High because of auger electron spectroscopy
Running cost Low as it’s a low temperature process
Working Area
Number of Labor
Comments
”Aluminum thin film growth by the thermal decomposition of triethylamine alane”, Lawrence H.Dubois, Bernard R. Zegarski,
Mihal E. Gross and Ralph G. Nuzzo, Surface Science 244(1991) 89-95, [164]
182
Table 151: Conventional technology to destroy Methanol
METHANOL
Items to compare
Conventional technology
Destruction technology Decomposition of Methanol over a series of bimetallic Pt-M catalysts with M=Au,Pd,Ru,Fe
Efficiency
Amount of destruction
By Products PtO, PtO2
Skilled Labor Yes
Dangerous process No
Automatic Not completely
PTOTMBD No
PTODABD Yes
Investment cost High because of XPS, AFM, TEM, Mass spectrometery, Packed-bed mass flow reactor
Running cost High
Working Area Large
Number of Labor 1
Comments
”Bimetallic Pt-Metal catalysts for the decomposition of methanol: Effect of secondary metal on the oxidation state, activity and
selectivity of Pt”, Jason R.Croy, S.Mostafa, L.Hickman, H.Heinrich, B.Roldan Cuenya, Applied Catalysis A: General 350(2008) 207-
216, [165]
Table 152: Conventional technology to destroy Ethanol
ETHANOL
Items to compare
Conventional technology
Destruction technology
Catalytic decomposition of ethanol on V2O5/AlPO4 catalysts
Efficiency More than 97%
Amount of destruction
By Products Ethene
Skilled Labor Yes
Dangerous process No
Automatic Not completely
PTOTMBD Yes
PTODABD Yes
Investment cost High because of TG, DTG, DSC, X-ray diffraction
Running cost High because of temp (500 °C)
Working Area Large
Number of Labor 1
Comments The higher degree of conversion of ethanol to ethane for the samples
183
containing V2O5 may not only be due to the optimum ration of V4+/V5+ but also due to the value of the activation energy of charge carriers
”Catalytic decomposition of ethanol on V2O5/AlPO4 catalysts”, Abd El-Aziz A Said, Kamal MS Khalil, J Chem Technol Biotechnol
75: 196-204 (2000), [166]
Table 153: Conventional technology to destroy Isopropanol
ISOPROPANOL
Items to compare
Conventional technology
Destruction technology Decomposition of isopropanol by heteropolyanion-doped polyanilines
Efficiency
Amount of destruction
By Products Acetone, propene
Skilled Labor
Dangerous process
Automatic
PTOTMBD Yes as it was diluted with Nitrogen
PTODABD Yes
Investment cost
Running cost
Working Area
Number of Labor
Comments
”Catalytic decomposition of isopropanol over polyaniline doped by heteropolyanions”, W.Turek, M. Lapkowski, G. Bidan,
Materials Science Forum Vol.122 (1993) pp.65-76, [167]
Table 154: Conventional technology to destroy Methanol
METHANOL
Items to compare
Conventional technology
Destruction technology
Decomposition of methanol over single and different bimetallic exchange combinations of Co, Cr, Cu and Zeolite Beta using a fixed-bed catalytic reactor in temp range of 100-500 °C
Efficiency 90% over 350 °C
Amount of destruction
By Products CO2, CO
Skilled Labor Yes
Dangerous process No but care is required to deal with compressor
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High because of BET, compressor, gas chromatographer, reactor
184
Running cost Moderate
Working Area Small
Number of Labor 1
Comments 100% conversion over 450 °C
”Catalytic decomposition of methanol in air over different combinations of bimetallic exchanged H-Bea Zeolite with Cobalt,
chromium and Copper”, Ahmad Zuhairi Abdullah, Mohamad Zailani Abu Bakar and Subhash Bhatia, Journal of Industrial
Technology 11 (2), 2002, 47-55, [168]
Table 155: Conventional technology to destroy Methylene chloride
METHYLENE CHLORIDE
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of methylene chloride in air with a concentration of 959 ppm and 160-275 °C with three different sulfated oxide catalysts
Efficiency 100% using sulfated Titanium dioxide catalyst
Amount of destruction
By Products HCl, CO, CO2
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High because of fixed bed reactor, mass flow controller, gas chromatographer, thermogravimeteric analyzer
Running cost Very high
Working Area Lab Scale Large
Number of Labor 1
Comments
”Catalytic decomposition of methylene chloride by sulfated oxide catalysts”, Xuan-Zhen Jiang, Li-Qing Zhang, Xiao-Hua Wu, Lei
Zheng, Applied Catalysis B: Environmental 9(1996) 229-237, [169]
Table 156: Conventional technology to destroy Methylene chloride
METHYLENE CHLORIDE
Items to compare
Conventional technology
Destruction technology
Decomposition of methylene chloride using chromium oxide catalysts with the help of TGA and XPS
Efficiency
Amount of destruction
By Products HCl, CO, CO2
Skilled Labor Yes
Dangerous No
185
process
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High because of XPS, TGA, BET, TPD, fixed bed reactor
Running cost High as prolonged heating at high temperature
Working Area Lab Scale Large
Number of Labor 1
Comments
”Catalytic decomposition of methylene chloride on oxidative carbon supported metal oxide catalysts 2. Chromium oxide
catalyst”, Min Kang, Min Woo song and Chang Ha Lee, React. Kinet.Catal. Lett. Vol.80, No.1, 131-138, [170]
Table 157: Conventional technology to destroy Methylene Chloride
METHYLENE CHLORIDE
Items to compare
Conventional technology
Destruction technology
Decomposition of methylene chloride using Cobalt oxide catalysts with the help of BET, XRD, TGA
Efficiency
Amount of destruction
By Products HCl, CO, CO2
Skilled Labor Yes
Dangerous process
No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High because of BET, XRD, TGA, chromatographers
Running cost High as prolonged heating at high temp
Working Area Lab Scale Large
Number of Labor 1
Comments
”Catalytic decomposition of methylene chloride on oxidative carbon supported metal oxide catalysts 1. Cobalt Oxide Catalyst”,
Min Kang, Min Woo song and Chang Ha Lee, React. Kinet. Catal. Lett. Vol.80, No.1, 123-129, [171]
Table 158: Conventional technology to destroy N-Heptane
N-HEPTANE
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of n-heptane for the growth of high quality single wall carbon nanotubes
Efficiency
Amount of destruction
186
By Products
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High as it is used TEM, spectrometer
Running cost High as it involves high temperatures
Working Area Lab Scale Large
Number of Labor 1
Comments
”Catalytic decomposition of n-heptane for the growth of high quality single wall carbon nanotubes”, D. Grimm, A.Gruneis, C.
Kramberger, M.Rummeli, T.Gemming, B.Buchner, M.Rummeli, T.Gemming, B.Buchner, A.Barreiro, H.Juzmany, R.Pfeiffer,
T.Pichler, Chemical Physics Letter 428 (2006) 416-420, [172]
Table 159: Conventional technology to destroy Toulene
TOULENE
Items to compare
Conventional technology
Destruction technology Catalytic decomposition of toluene using various dielectric Barrier Discharge Reactors
Efficiency 95%
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost Moderate
Working Area Small
Number of Labor 1
Comments Use of in-plasma catalysis were more helpful to enhance the destruction and removal efficiency and reducing the O3 formation than that of either post-plasma catalysis or plasma alone
”Catalytic decomposition of toulene using various dielectric Barrier Discharge Reactors”, YE Daiqi, Huang Haibao, Chen Weili,
Zeng Ronghui, Plasma Science and Technology, Vol.10, No.1, Feb 2008, [173]
Table 160: Conventional technology to destroy Methanol
METHANOL
Items to compare
Conventional technology
Destruction technology Decomposition of methanol at 250 °C using nickel-silica composites
187
prepared by sol gel method
Efficiency 64.10%
Amount of destruction
By Products CO, H2, CH4, H2O
Skilled Labor Yes but just for analytical equipments
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High because of XRD, BET, chromatographer
Running cost High because of high temp (400 °C for 5 hours)
Working Area Lab Scale Large
Number of Labor 1
Comments
”Catalytic methanol decomposition to carbon monoxide and hydrogen over Ni/SiO2 of high nickel content”, Yasuyuki
Matsumura, Naoki Tode, Tetsuo Yazawa, Masatake Haruta, Journal of Molecular Catalysis A: Chemical 99(1995) 183-185, [174]
Table 161: Conventional technology to destroy Propylene Carbonate
PROPYLENE CARBONATE
Items to compare
Conventional technology
Destruction technology Decomposition of propylene carbonate at graphite electrode in 1 M LiClO4 employing a variety of transient electrochemical techniques
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process Yes
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost Moderate
Running cost Low
Working Area Small
Number of Labor 1
Comments
”Cathodic Decomposition of Propylene Carbonate at Graphite Electrodes2, Tiehua Piao, Chil Hon Doh, Sung In Moon and Su-
Moon Park, Battery Conference on Applications and Advances, 1997, Twelfth Annual, DOI: 10.1109/BCAA.1997.574113, [175]
Table 162: Conventional technology to destroy N-Propyl amine, Diethylamide and Triethylamine
N-PROPYLAMINE,DIETHYLAMINE AND TRIETHYLAMINE
Items to compare
Conventional technology
Destruction technology Decomposition over ZrO2, SiO2-Al2O3 and MgO studied by temperature
188
programmed desorption and catalytic conversion
Efficiency 95.8% for n-propyl amine, 63.5% for diethyl amine, 88% for triethylamine
Amount of destruction
By Products Acetonitrile
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD Yes
PTODABD Yes
Investment cost High because of XRD, BET, spectrometer, gas chromatographer
Running cost High as catalyst preparation demands 873 K for 24 hours
Working Area Large
Number of Labor 1
Comments
”Characteristic Action of Zirconium Dioxide in the Decomposition of Alkyl amines”, B.Q XU, T.Yamaguchi and K.Tanabe, Applied
Catalysis, 64(1990) 41-54, [176]
Table 163: Conventional technology to destroy Benzene and Toulene
BENZENE AND TOULENE
Items to compare
Conventional technology
Destruction technology Decomposition of Benzene, toluene and particulate condensed matter by the use of thermally excited holes in TiO2 at high temperatures
Efficiency 100%
Amount of destruction
By Products H2O and CO2 at 350 °C
Skilled Labor Yes
Dangerous process No but it can become if autoclave is not used properly
Automatic Yes
PTOTMBD Yes
PTODABD Yes
Investment cost High because of autoclave, DSC, TGa, spectrophotometer, spectrometer
Running cost Moderate
Working Area Lab Scale Large
Number of Labor 1
Comments
”Complete decomposition of Benzene, Toulene and Particulate Matter Contained in the exhaust of diesel engines by means of
thermally excited holes in Titanium Dioxide at high temperatures”, Takashi Makino, Keiji Matsumoto, Toru Ebara, Takashi Mine,
Takumi Ohtsuka and Jin Mizuguchi, Japanese Journal of Applied Physics Vol.46, No.9A, 2007, pp.6037-6042, [177]
Table 164: Conventional technology to destroy Toulene
TOULENE
Items to compare
Conventional technology
189
Destruction technology
Decomposition of toluene using UV light from plasma and an external UV lamp in a dielectric barrier discharge plasma/UV system, as well as in a plasma/photo catalysis system
Efficiency 73%
Amount of destruction
By Products CO, CO2, benzene, toluene
Skilled Labor Yes
Dangerous process Yes
Automatic Yes
PTOTMBD Yes
PTODABD Yes
Investment cost High because of plasma reactor, gas chromatographer, spectrometer
Running cost Moderate
Working Area Lab Scale Large
Number of Labor 1
Comments UV light from DBD reactor was very weak. Introduction of external UV light to the plasma significantly improves the removal efficiency of toluene by 20%
”Contribution of UV light to the decomposition of toulene in dielectric barrier discharge plasma/photo catalysis system”, Hai Bao
Huang, Dai Qi Ye, Ming Li Fu, Fa Da Feng, Plasma Chem Plasma Process (2007) 25:577-588, DOI: 10.1007/s11090-007-9085-z,
[178]
Table 165: Conventional technology to destroy Acetic Acid
ACETIC ACID
Items to compare
Conventional technology
Destruction technology Acetic acid efficiently decomposed within 120 mins of UV radiation and with different oxidation processes such as TiO2-UV-H2O2,Fe-H2O2-UV,UV-H2O2 and TiO2-UV
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No but laser safety precautions should be ensured
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost Moderate
Running cost Low
Working Area Lab Scale Small
Number of Labor 1
Comments Decomposition efficiency of acetic acid was fastest in the UV-H2O2 process
”Decomposition of acetic acid by advanced oxidation processes”, Ju Young Park and In Hwa Lee”, Korean J.Chem.Eng. 26(2),
387-391 (2009), [179]
190
Table 166: Conventional technology to destroy Acetone
ACETONE
Items to compare
Conventional technology
Destruction technology Photo catalytic decomposition UV/TiO2 of gaseous acetone with a fixed-bed annular reactor using TiO2 as the photo catalyst at room temperature
Efficiency
Amount of destruction
By Products CO2, H2O
Skilled Labor Yes
Dangerous process No but laser safety precautions should be ensured
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost High because of BET, FESEM, flow meter, flow controller, mass flow meter
Running cost Low
Working Area Lab Scale Large
Number of Labor 1
Comments In this study, the direct photolysis of acetone in air stream by 365 nm UV irradiation was studied and the decomposition of acetone was found to be negligible. Decomposition was increased by increasing UV Intensity
“Decomposition of gaseous acetone in an annular photo reactor coated with TiO2 thin film”, Young Ku, Kun-Yu Tseng and Wen-
Yu Wang, Water, Air and Soil Pollution, Volume 168, Numbers 1-4, 313-323, DOI:10,1007/s11270-005-1778-4, [180]
Table 167: Conventional technology to destroy Methanol
METHANOL
Items to compare
Conventional technology
Destruction technology Plasma decomposition of methanol using AC and DC corona discharges at ambient condition
Efficiency 80%
Amount of destruction
By Products H2, CO, CO2
Skilled Labor Yes
Dangerous process Safer than other technologies
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost Moderate
Running cost Cheap
Working Area Lab Scale
Number of Labor 1
191
Comments A major advantage of methanol decomposition using corona discharge is that only a very small discharge space is enough for sufficiently high decomposition
”Novel Plasma Methanol Decomposition to Hydrogen Using Corona Discharges”, Hui-qing Li, Ji-jun Zou, Yue-ping Zhang, Chang-
jun Liu, Chemistry Letters Vol.33, No. 6(2004), [181]
Table 168: Conventional technology to destroy Isopropanol
ISOPROPANOL
Items to compare
Conventional technology
Destruction technology Decomposition of isopropanol over V2O5 using UV-visible photo irradiation
Efficiency
Amount of destruction
By Products Propene, H2O
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost Low
Working Area Lab Scale Large
Number of Labor 1
Comments
”Photo enhanced catalytic decomposition of isopropanol on V2O5”, A.Z.Moshfegh and A.lgnatiev, Catalysis Letters 4 (1990) 113-
122, [182]
Table 169: Conventional technology to destroy Toulene
TOULENE
Items to compare
Conventional technology
Destruction technology Photo catalytic decomposition of toluene over TiO2 nanoparticles embedded on activated carbon
Efficiency 98%
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High
192
Running cost Low
Working Area Lab Scale Large
Number of Labor 1
Comments
”Photocatalytic decomposition of gaseous toulene by TiO2 nanoparticles coated on activated carbon”, A.Rezaee,
Gh.H.Pourtaghi, A.Khavanin, R.Sarraf Mamoory, M.T. Ghaneian, H.Godini,
Iran.J.Environ.Helath.Sci.Eng,.2008,Vol.5,No.4,pp.305-310, [183]
Table 170: Conventional technology to destroy Methyl Tert-Butyl Ether
METHYL TERT-BUTYL ETHER
Items to compare
Conventional technology
Destruction technology Photo catalytic decomposition of methyl tert-butyl ether in aqueous slurry of TiO2 particles irradiated with Xe Lamp in a batch reactor
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD Yes as the solution is made
PTODABD No
Investment cost Moderate
Running cost Low
Working Area Lab Scale Small
Number of Labor 1
Comments
”Photo catalytic decomposition of methyl tert-butyl ether in aqueous slurry of titanium dioxide”, Yujing Zhang, Ramin Farnood,
Applied Catalysis B: Environmental 57(2005) 275-282, [184]
Table 171: Conventional technology to destroy Acetic Acid
ACETIC ACID
Items to compare
Conventional technology
Destruction technology Decomposition of acetic acid photo catalytically on TiO2 in an inert atmosphere by two parallel pathways at room temperature
Efficiency
Amount of destruction
By Products CO2, C2H6, CH4, H2O
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
193
PTODABD No
Investment cost High
Running cost High
Working Area Small
Number of Labor 1
Comments
”Photo catalytic decomposition of acetic acid on TiO2”, Darrin S. Muggli, Sarah A.Keyser and John L.Falconer, Catalysis Letters
55(1998) 129-132, [185]
Table 172: Conventional technology to destroy Acetic Acid
ACETIC ACID
Items to compare
Conventional technology
Destruction technology Decomposition of acetic acid using UV light and thin films of TiO2 and TiO2/SiO2
Efficiency
Amount of destruction
By Products H2O, CO2
Skilled Labor Yes
Dangerous process No
Automatic No
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost High
Working Area Large
Number of Labor 1
Comments TiO2/SiO2 thin film having a pure-anatase phase showed a higher photo catalytically activity than did the pure-anatase SiO2
”Photo catalysis decomposition of acetic acid over TiO2 and TiO2/SiO2 thin films prepared by the Sol Gel Method”, Man Sig Lee,
Ju Dong Lee and Seong Soo Hong, J.Ind.Eng.Chem.Vol 11, No.4, (2005) 459-501, [186]
Table 173: Conventional technology to destroy Formic Acid
FORMIC ACID
Items to compare
Conventional technology
Destruction technology Decomposition of formic acid photo catalytically by V-ions implantation into TiO2 thin film
Efficiency 100%
Amount of destruction
By Products CO2, H2O
Skilled Labor Yes
Dangerous process No
Automatic Yes
194
PTOTMBD No
PTODABD Yes
Investment cost Very high because of XRD, UV-vis, XPS, FE-SEM, AFM, Spectrometer
Running cost High
Working Area Large
Number of Labor 1
Comments
”Photo catalytic decomposition of formic acid under visible light irradiation over V-ion implanted TiO2 thin film photo catalysts
prepared on quartz substrated by ionized cluster beam(ICB) deposition method”, Jinkai Zhou, Masato Takeuchi, X.S.Zhao, Ajay
K.Ray, Masakazu Anpo, Catalysis Letters Vol.106, Nos.1-2, January 2006, DOI: 10.1007/s10562-005-91921-5, [187]
Table 174: Conventional technology to destroy Toulene
TOULENE
Items to compare
Conventional technology
Destruction technology Photo catalytic decomposition of toluene over TiO2 film, prepared by sol-gel method and coated on porous nickel
Efficiency Yes
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost Low
Working Area Small
Number of Labor 1
Comments Toulene can be decomposed effectively by this method
”Photo catalytic decomposition of toulene by TiO2 filmed as photo catalyst”, Xiaodong Duan, Dezhi Sun, Zhibin Zhu, Xiangqun
Chen, Pengfei Shi, J.Environ.Sci.Helath, A37(4), 679-692(2002) , [188]
Table 175: Conventional technology to destroy LaTi(O,N)3
LaTi(O,N)3
Items to compare
Conventional technology
Destruction technology Photo catalytic activity of LaTi(O,N)3 nanoparticles for the gas phase decomposition of acetone under visible light
Efficiency
Amount of destruction
By Products CO2, H2O
Skilled Labor Yes
195
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High because of XRD, TEM, BET, UV-V spectroscopy
Running cost High as catalyst preparation is very expensive
Working Area Large
Number of Labor 1
Comments Catalyst preparation is very expensive in this experiment
”Photo catalytic decomposition of acetone using LaTi(O,N)3 nanoparticles under visible light irradiation”, Rosiana Aguiar,
Andreas Kalytta, Armin Reller, Anke Weidenkaff, Stefan G. Ebbinghaus, Journal of Materials Chemistry, DOI: 10.1039/b806794e,
[189]
Table 176: Conventional technology to destroy Benzene
BENZENE
Items to compare
Conventional technology
Destruction technology Photo catalytic decomposition of benzene over TiO2 in the gas phase at room temperature using a fixed bed flow reactor in a humified airstream
Efficiency 100%
Amount of destruction
By Products CO2, CO, benzene, phenol
Skilled Labor Yes
Dangerous process No but can become if cylinders are not safe
Automatic Yes
PTOTMBD Yes as the reaction gas was made
PTODABD Yes as it was pre-heated
Investment cost Moderate
Running cost Moderate
Working Area Lab Scale/Small
Number of Labor 1
Comments
”Photo catalytic decomposition of benzene over TiO2 in a humified airstream”, Hiahiro Einaga, Shigeru Fuamura and Takaashi
Ibusuki, Chem.Chem.Phys.1999, 1, 4903-4908, [190]
Table 177: Conventional technology to destroy HCCl3
HCCl3
Items to compare
Conventional technology
Destruction technology Photo catalytic decomposition of HCCl3 in a fully irradiated photo reactor by varying the concentrations of chloroform, dissolved oxygen, titania, the local volumetric rate of energy absorption using titanium oxide particulate suspensions
196
Efficiency
Amount of destruction
By Products
Skilled Labor Yes
Dangerous process
Automatic No
PTOTMBD No
PTODABD No
Investment cost Moderate
Running cost Moderate
Working Area Small
Number of Labor 1
Comments
”Photo catalytic decomposition of chloroform in a fully irradiated heterogeneous photo reactor using titanium oxide particulate
suspensions”, Carlos A.Martin, Miguel A.Baltanas, Alberto E.Cassano, Catalysis Today 27(1996) 221-227, [191]
Table 178: Conventional technology to destroy Gas Acetone
GAS ACETONE
Items to compare
Conventional technology
Destruction technology Gas acetone was decomposed in an annular photo reactor coated with TiO2 or Pt/TiO2 catalysts using a UV or a fluorescent lamp as light source
Efficiency 90%
Amount of destruction
By Products CO2
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD High
Investment cost Low
Running cost Lab Scale Large
Working Area 1
Number of Labor Almost complete decomposition and mineralization of gaseous acetone were accomplished for experiments conducted with higher UV light intensities
Comments
”Photocatalyic decomposition of gaseous acetone using TiO2 and Pt/TiO2 catalysts”, Young Ku, Kun-Yu Tseng, Chih-Ming Ma,
International Journal of Chemical Kinetics-INT J CHEM KINET, Vol 40, no.4, pp.209-216, [192]
Table 179: Conventional technology to destroy Ftetrachloroethylene
FTETRACHLOROETHYLENE
Items to compare
Conventional technology
197
Destruction technology
Gas phase photo catalytic destruction of tetrachloroethylene by using an in situ photo catalytic reactor with FT-IR analysis in batch mode, using TiO2 as catalyst
Efficiency
Amount of destruction
By Products CO2, COCl2(phosgene)
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No but just preheating
Investment cost Moderate
Running cost Low
Working Area Small
Number of Labor 1
Comments
”Photo catalytic decomposition of tetrachloro-ethylene in the gas phase with titanium dioxide as catalyst”, Marta Hegedus,
Andras Dombi and Imre Kiricsi, React. Kinet.Catal.Lett.Vol.74, No.2, 209-215(2001), [193]
Table 180: Conventional technology to destroy Acetic Acid5
ACETIC ACID
Items to compare
Conventional technology
Destruction technology Photo catalytic oxidation and decomposition of acetic acid over TiO2, TS-1 and Ti-MCM-41 catalysts
Efficiency
Amount of destruction
By Products CO2, CH4, C2H6 for P-25 TiO2, CO2, CH4 for TS-1 and Ti-MCM-41
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD Yes
Investment cost High
Running cost Moderate
Working Area Large
Number of Labor 1
Comments
”Photo catalytic oxidation and decomposition of acetic acid over TiO2, TS-1 and Ti-MCM-41 catalysts”, J.H.Park, S.G. Kim, S.S.
Park, S.S. Hong and G.D. Lee, Materials Science Forum Vols. 510-511(2006) pp. 34-37, [194]
Table 181: Conventional technology to destroy Diethyl Ketone
DIETHYL KETONE
198
Items to compare
Conventional technology
Destruction technology Decomposition of diethyl ketone by IR-laser and comparing with SiF4-sensitized decomposition of diethyl ketone and n-butane
Efficiency 100%
Amount of destruction
By Products CO, H2, CH4, C2H6, C2H4, C3H8, C2H2, C3H6, C4H10
Skilled Labor Yes
Dangerous process No
Automatic Yes
PTOTMBD No
PTODABD No
Investment cost Moderate
Running cost High as it’s high temperature process
Working Area Small
Number of Labor 1
Comments
”IR Laser-Induced decomposition of diethyl ketone and n-butane”, W. Braun, J.R. Mcnesby and M.J. Pilling, Journal of
Photochemistry, 17 (1981) 281-295, [195]
Table 182: Conventional technology to destroy Ethanol
ETHANOL
Items to compare
Conventional technology
Destruction technology Infrared multiphoton absorption and decomposition of ethanol vapor
Efficiency
Amount of destruction
By Products H2O, C2H4 through other channels, CH3CHO, C2H6, CH4, C2H2
Skilled Labor Yes
Dangerous process No
Automatic
PTOTMBD Yes
PTODABD No
Investment cost Moderate
Running cost High as it’s a high temperature process
Working Area Small
Number of Labor 1
Comments
”Infrared multiphoton adsorption and decomposition of ethanol vapour”, R.A. Back, D.K. Evans, Robert D.Mcalpine, E.M.
Verpoorte, Mike Ivanco, J.W. Goodale, H.M.Adams, Can.J.Chem.66,857 (1988) , [196]
199
4. Liquids
4.1 Sulfuric Acid, H2SO4
Energy required to decompose H2SO4 [197] is demonstrated using Hess’s Law
Eqn1 H2S (g) + 2O2 (g) → H2SO4 (l) ΔH= -235.5 kJ
Eqn2 H2S (g) + 2O2 (g) → SO3 (g) + H2O (l) ΔH= -207 kJ
Eqn3 H2O (l) → H2O (g) ΔH= 44 kJ
Reverse Eqn1=> H2SO4 (l) → H2S (g) + 2O2 (g) ΔH= 235.5 kJ
Eqn2=> H2S (g) + 2O2 (g) → SO3 (g) + H2O (l) ΔH= -207 kJ
Eqn3=> H2O (l) → H2O (g) ΔH= 44 kJ
H2SO4 (l) → SO3 (g) + H2O (g) ΔH= 72 kJ/mol [197]
4.2 Nitric Acid, HNO3
Energy required to decompose HNO3 [201] is demonstrated using Hess’s Law
Eqn1 2N2 (g) + 5O2 (g) → 2N2O5 (g) ΔH= 6.8 kcal/mol
Eqn2 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -136.6 kcal/mol
Eqn3 N2O5 (g) + H2O (l) → 2HNO3 (l) ΔH= -18.3 kcal/mol
Eqn1=> 2N2 (g) + 5O2 (g) → 2N2O5 (g) ΔH= 6.8 kcal/mol
Eqn2=> 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -136.6 kcal/mol
Eqn3 x 2=> 2N2O5 (g) + 2H2O (l) → 4HNO3 (l) ΔH= -36.6 kcal/mol
2H2 (g) + 2N2 (g) + 6O2 (g) → 4HNO3 (l) ΔH= -166.4 kcal/mol
HNO3 (l) → 1/2H2 (g) + 1/2N2 (g) + 3/2O2 (g) ΔH= 174 kJ/mol [201]
200
4.3 Acetic Acid, CH3COOH
Energy required to decompose CH3COOH [202] is demonstrated using Hess’s Law
Eqn1 CH3COOH (l) + 2O2 (g) → 2CO2 (g) + 2H2O (l) ΔH= -875 kJ/mol
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Reverse Eqn1=>2CO2 (g) + 2H2O (l) → CH3COOH (l) + 2O2 (g) ΔH= 875 kJ/mol
Eqn2 x 2=> 2C (s) + 2O2 (g) → 2CO2 (g) ΔH= -789.02 kJ/mol
Eqn3 x2=> 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -571.6 kJ/mol
2C (s) + 2H2 (g) + O2 (g) → CH3COOH (l) ΔH= -485 kJ/mol
CH3COOH (l) → 2C (s) + 2H2 (g) + O2 (g) ΔH= 485 kJ/mol [202]
4.4 Hydrochloric Acid, HCl
Energy required to decompose HCl [203] is demonstrated using Hess’s Law
Eqn1 NH3 (g) + HCl (g) → NH4Cl (s) ΔH= -176 kJ
Eqn2 N2 (g) + 3H2 (g) → 2NH3 (g) ΔH= -92.2 kJ
Eqn3 N2 (g) + 4H2 (g) + Cl2 (g) → 2NH4Cl (s) ΔH= -628.86 kJ
Reverse Eqn1 x 2=> 2NH4Cl (s) → 2NH3 (g) + 2HCl (g) ΔH= 352 kJ
Reverse Eqn2=> 2NH3 (g) → N2 (g) + 3H2 (g) ΔH= 92.2 kJ
Eqn3=> N2 (g) + 4H2 (g) + Cl2 (g) → 2NH4Cl (s) ΔH= -628.86 kJ
H2 (g) + Cl2 (g) → 2HCl (g) ΔH= -184.66 kJ
HCl (g) → 1/2H2 (g) + 1/2Cl2 (g) ΔH= 92.33 kJ/mol [203]
201
4.5 Hydrogen Bromide, HBr
Energy required to decompose HBr [204] is demonstrated using Hess’s Law
Eqn1 2C + 2H2 → C2H4 ΔH= 52.2 kJ/mol
Eqn2 C2H4 + HBr → C2H5Br ΔH= -106.3 kJ/mol
Eqn3 2C + 5/2H2 + 1/2Br2 → C2H5Br ΔH= -90.5 kJ
Reverse Eqn2=> C2H5Br → C2H4 + HBr ΔH= 106.3 kJ/mol
Eqn3=> 2C + 5/2H2 + 1/2Br2 → C2H5Br ΔH= -90.5 kJ
Reverse Eqn1=> C2H4 → 2C + 2H2 ΔH= -52.3 kJ/mol
1/2H2 + 1/2Br2 → HBr (l) ΔH= -36.4 kJ/mol
HBr (l) → 1/2H2 + 1/2Br2 ΔH= 36.4 kJ/mol [204]
4.6 Hydrogen Iodide, HI
Energy required to decompose HI [205] is demonstrated using Hess’s Law
Eqn1 I2 (g) → I2 (s) ΔH= -124.8 kJ
Eqn2 3I2 (g) + 3H2 (g) → 6HI (g) ΔH= -219 kJ
Eqn2/3=> I2 (g) + H2 (g) → 2HI (g) ΔH= -73 kJ
Reverse Eqn1=> I2 (s) → I2 (g) ΔH= 124.8 kJ
H2 (g) + I2 (g) → 2HI (g) ΔH= 51.8 kJ
HI (g) → 1/2H2 (g) + 1/2I2 (s) ΔH= -26 kJ/mol [205]
202
4.7 Boric Acid, H3BO3
Energy required to decompose H3BO3 [206] is demonstrated using Hess’s Law
Eqn1 H3BO3 (aq) → HBO2 (aq) + H2O (l) ΔH= -.02 kJ
Eqn2 H2B4O7 (aq) + H2O (l) → 4HBO2 (aq) ΔH= -11.3 kJ
Eqn3 H2B4O7 (aq) → 2B2O3 (s) + H2O (l) ΔH= 17.5 kJ
Reverse Eqn1 x 4=> 4HBO2 (aq) + 4H2O (l) → 4H3BO3 (aq) ΔH= .02 kJ
Reverse Eqn3=> 2B2O3 (s) + H2O (l) → H2B4O7 (aq) ΔH= -17.5 kJ
Eqn2=> H2B4O7 (aq) + H2O (l) → 4HBO2 (aq) ΔH= -11.3 kJ
2B2O3 (s) + 6H2O (l) → 4H3BO3 (aq) ΔH= -28.78 kJ
H3BO3 (aq) → 1/2B2O3 (s) + 3/2H2O (l) ΔH= 7.195 kJ/mol [206]
4.8 Oxalic Acid, C2H2O4
Energy required to decompose C2H2O4 [207] is demonstrated using Hess’s Law
Eqn1 C2H2O4 (s) + 1/2O2 (g) → 2CO2 (g) + H2O (l) ΔH= -822.2 kJ/mol
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Reverse Eqn1=>2CO2 (g) + H2O (l) → C2H2O4 (s) + 1/2O2 (g) ΔH= 822.2 kJ/mol
Eqn2 x 2=> 2C (s) + 2O2 (g) → 2CO2 (g) ΔH= -789.02 kJ/mol
Eqn3=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
2C (s) + H2 (g) + 2O2 (g) → C2H2O4 (s) ΔH= -252.62 kJ/mol
C2H2O4 (s) → 2C (s) + H2 (g) + 2O2 (g) ΔH= 252.62 kJ/mol [207]
203
4.9 Formic Acid, HCOOH
Energy required to decompose HCOOH [208] is demonstrated using Hess’s Law
Eqn1 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol
Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Eqn3 HCOOH (l) + 1/2O2 (g) → CO2 (g) + H2O (l) ΔH= -275 kJ
Reverse Eqn3=>CO2 (g) + H2O (l) → HCOOH (l) + 1/2O2 (g) ΔH= 275 kJ
Eqn1=> C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol
Eqn2=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
C (s) + O2 (g) + H2 (g) → HCOOH (l) ΔH= -405.31 kJ/mol
HCOOH (l) → C (s) + O2 (g) + H2 (g) ΔH= 405.31 kJ/mol [208]
4.10 Citric Acid, C6H8O7
Energy required to decompose C6H8O7 [209] is demonstrated using Hess’s Law
Eqn1 C6H8O7 (s) + 9/2O2 (g) → 6CO2 (g) + 4H2O (g) ΔH= -1950 kJ/mol
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (g) ΔH= -241.8 kJ/mol
Reverse Eqn1=>6CO2 (g) + 4H2O (g) → C6H8O7 (s) + 9/2O2 (g) ΔH= 1950 kJ/mol
Eqn2 x 6=> 6C (s) + 6O2 (g) → 6CO2 (g) ΔH= -2367 kJ/mol
Eqn3 x 4=> 4H2 (g) + 2O2 (g) → 4H2O (g) ΔH= -967.2 kJ/mol
6C (s) + 4H2 (g) + 7/2O2 (g) → C6H8O7 (s) ΔH= -1384 kJ/mol
C6H8O7 (s) → 6C (s) + 4H2 (g) + 7/2O2 (g) ΔH= 1384 kJ/mol [209]
204
4.11 Benzoic Acid, C7H6O2
Energy required to decompose C7H6O2 [207] is demonstrated using Hess’s Law
Eqn1 C7H6O2 (s) + 15/2O2 (g) → 7CO2 (g) + 3H2O (l) ΔH= -3226.9 kJ/mol
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Eqn1=> C7H6O2 (s) + 15/2O2 (g) → 7CO2 (g) + 3H2O (l) ΔH= -3226.9 kJ/mol
Reverse Eqn2 x 7=> 7CO2 (g) → 7C (s) + 7O2 (g) ΔH= 2754.57 kJ/mol
Reverse Eqn2 x 3=> 3H2O (l) → 3H2 (g) + 3/2O2 (g) ΔH= 857.4 kJ/mol
C7H6O2 (s) → 7C (s) + 3H2 (g) + O2 (g) ΔH= 385.07 kJ/mol [207]
4.12 Hydrogen Peroxide, H2O2
Energy required to decompose H2O2 [210] is demonstrated using Hess’s Law
Eqn1 H2O2 (l) → H2O (l) + 1/2O2 (g) ΔH= -98.2 kJ/mol
Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Reverse Eqn1=> H2O (l) + 1/2O2 (g) → H2O2 (l) ΔH= 98.2 kJ/mol
Eqn2=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
H2 (g) + O2 (g) → H2O2 (l) ΔH= -187.6 kJ/mol
H2O2 (l) → H2 (g) + O2 (g) ΔH= 187.6 kJ/mol [210]
205
4.13 Ammonia, NH3
Energy required to decompose NH3 [211] is demonstrated using Hess’s Law
Eqn1 2CH4 (g) → 2C (s) + 4H2 (g) ΔH= 149.8 kJ
Eqn2 H2 (g) + 2C (s) + N2 (g) → 2HCN (g) ΔH= 270.3 kJ
Eqn3 CH4 (g) + NH3 (g) → HCN (g) + 3H2 (g) ΔH= 255.95 kJ
Reverse Eqn3 x 2=>2HCN (g) + 6H2 (g) → 2CH4 (g) + 2NH3 (g) ΔH= -511.9 kJ
Eqn1=> 2CH4 (g) → 2C (s) + 4H2 (g) ΔH= 149.8 kJ
Eqn2=> H2 (g) + 2C (s) + N2 (g) → 2HCN (g) ΔH= 270.3 kJ
N2 (g) + 3H2 (g) → 2NH (g) ΔH= -92.1 kJ
NH3 (g) → 1/2N2 (g) + 3/2H2 (g) ΔH= 46.05 kJ/mol [211]
4.14 Calcium Hydroxide, Ca(OH)2
Energy required to decompose Ca (OH) 2[212] is demonstrated using Hess’s Law
Eqn1 CaO (s) + H2O (l) → Ca(OH)2 (s) ΔH= -15.260 kcal/mol
Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -68.370 kcal/mol
Eqn3 Ca (s) + 1/2O2 (g) → CaO (s) ΔH= -151.8 kcal/mol
Eqn1=> CaO (s) + H2O (l) → Ca(OH)2 (s) ΔH= -15.260 kcal/mol
Eqn2=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -68.370 kcal/mol
Eqn3=> Ca (s) + 1/2O2 (g) → CaO (s) ΔH= -151.8 kcal/mol
Ca (s) + O2 (g) + H2 (g) → Ca(OH)2 (s) ΔH= -235.43 kcal/mol= -985 kJ/mol
Ca(OH)2 (s) → Ca (s) + O2 (g) + H2 (g) ΔH= 985 kJ/mol [212]
206
4.15 Calcium Oxide, CaO
Energy required to decompose CaO[212] is demonstrated using Hess’s Law
Eqn1 CaO (s) + H2O (l) → Ca (OH) 2 (s) ΔH= -15.260 kcal/mol
Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -68.370 kcal/mol
Eqn3 Ca (s) + O2 (g) + H2 (g) → Ca (OH) 2 (s) ΔH= -235.43 kcal/mol
Reverse Eqn1=> Ca(OH)2 (s) → CaO (s) + H2O (l) ΔH= 15.260 kcal/mol
Eqn3=> Ca (s) + O2 (g) + H2 (g) → Ca(OH)2 (s) ΔH= -235.43 kcal/mol
Reverse Eqn2=> H2O (l) → H2 (g) + 1/2O2 (g) ΔH= 68.370 kcal/mol
Ca (s) + 1/2O2 (g) → CaO (s) ΔH= -151.8 kcal/mol
CaO (s) → Ca (s) + 1/2O2 (g) ΔH= 635 kJ/mol [212]
4.16 Sodium Bicarbonate, NaHCO3
Energy required to decompose NaHCO3 [213] is demonstrated using Hess’s Law
Eqn1 NaHCO3 (s) → Na (s) + 1/2H2 (g) + C (s) + 3/2O2 (g) ΔH= 950.81 kJ/mol
Eqn2 2Na (s) + C (s) + 3/2O2 (g) → Na2CO3 (s) ΔH= -1130.68 kJ/mol
Eqn3 C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol
Eqn4 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Eqn1 x 2=> 2NaHCO3 (s) → 2Na (s) + H2 (g) + 2C (s) + 3O2 (g) ΔH= 1901.62 kJ/mol
Eqn2=> 2Na (s) + C (s) + 3/2O2 (g) → Na2CO3 (s) ΔH= -1130.68 kJ/mol
Eqn3=> C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol
Eqn4=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
207
2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l) ΔH= 91.63 kJ [213]
4.17 Sodium bicarbonate, NaHCO3
Energy required to decompose NaHCO3[213] is demonstrated using Hess’s Law
Eqn1 2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l) ΔH= 91.63 kJ/2mol
Eqn2 2Na (s) + C (s) + 3/2O2 (g) → Na2CO3 (s) ΔH= -1130.68 kJ/mol
Eqn3 C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol
Eqn4 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Eqn1=> 2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l) ΔH= 91.63 kJ/2mol
Reverse Eqn2=> Na2CO3 (s) → 2Na (s) + C (s) + 3/2O2 (g) ΔH= 1130.68 kJ/mol
Reverse Eqn3=> CO2 (g) → C (s) + O2 (g) ΔH= 393.5 kJ/mol
Reverse Eqn4=> H2O (l) → H2 (g) + 1/2O2 (g) ΔH= 285.8 kJ/mol
2NaHCO3 (s) → 2Na (s) + 2C (s) + H2 (g) + 3O2 (g) ΔH= 1901.61 kJ
NaHCO3(s) → Na (s) + C (s) + 1/2H2 (g) + 3/2O2 (g) ΔH= 950.8 kJ/mol [213]
4.18 Sodium Carbonate, Na2CO3
Energy required to decompose Na2CO3 [213] is demonstrated using Hess’s Law
Eqn1 NaHCO3 (s) → Na (s) + 1/2H2 (g) + C (s) + 3/2O2 (g) ΔH= 950.81 kJ/mol
Eqn2 2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l) ΔH= 91.63 kJ/2mol
Eqn3 C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol
Eqn4 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
208
Reverse Eqn1 x 2=>2Na (s) + H2 (g) + 2C (s) + 3O2 (g) → 2NaHCO3(s) ΔH= -1901.62 kJ/mol
Eqn2=> 2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l) ΔH= 91.63 kJ/2mol
Reverse Eqn3=> CO2 (g) → C (s) + O2 (g) ΔH= 393.5 kJ/mol
Reverse Eqn4=> H2O (l) → H2 (g) + 1/2O2 (g) ΔH= 285.8 kJ/mol
2Na (s) + C (s) + 3/2O2 (g) → Na2CO3 (s) ΔH= -1130.68 kJ/mol
Na2CO3 (s) → 2Na (s) + C (s) + 3/2O2 (g) ΔH= 1130.68 kJ/mol [213]
Lattice Dissociation Energy
The energy required when one mole of a solid ionic compound is converted into its constituents gaseous
ions, measured under standard conditions of temperature and pressure. [214]
Enthalpy of Hydration
The energy released when one mole of gaseous ions dissolved in excess water, measured under
standard conditions of temperature and pressure. [214]
Enthalpy of Solution
The energy changed which occurs when one mole of a substance dissolves in excess water, measured
under standard conditions of temperature and pressure. [214]
4.19 Barium Hydroxide, Ba(OH)2, Born Haber cycle
Energy required to decompose Ba(OH)2 [215] is demonstrated using Born Haber Cycle
ΔHsolution = ΔH hydration - ΔHlattice
ΔHsolution = ΔHhydration of Ba2+ + ΔHhydration of OH- - Lattice dissociation energy
ΔHsolution = (-1360)+ 2(-460)-(-1768)
209
ΔHsolution = -512kJ/mol [215]
Ba(OH)2 Lattice Energy Ba2+(g) + 2OH-(g)
ΔHsolution
ΔHhydration
Ba2+(aq) + 2OH-(aq)
Energy= Plank’s Constant x Frequency
4.20 Strontium Hydroxide, Sr(OH)2
Energy required to decompose Sr(OH)2 [215] is demonstrated using Born Haber Cycle
ΔHsolution = ΔH hydration - ΔHlattice
ΔHsolution = ΔHhydration of Sr2+ + ΔHhydration of OH- - Lattice dissociation energy
ΔHsolution = -1480 + 2(-460) - (-1894)
ΔHsolution = -506kJ/mol [215]
210
Sr(OH)2 Lattice Energy Sr2+(g) + 2OH-(g)
ΔHsolution
ΔHhydration
Sr2+(aq) + 2OH-(aq)
Energy= Plank’s Constant x Frequency
4.21 Aluminum Hydroxide, Al(OH)3
Energy required to decompose Al (OH) 3 [216] is demonstrated using Hess’s Law
Eqn1 Al2O3 (s) + 3H2O (g) → 2Al (OH) 3 (s) ΔH= -149 kJ/mol
Eqn2 H2 (g) + 1/2O2 (g) → H2O (g) ΔH= -241.6 kJ/mol
Eqn3 2Al (s) + 3/2O2 (g) → Al2O3 (s) ΔH= -1676 kJ/mol
Eqn1=> Al2O3 (s) + 3H2O (g) → 2Al (OH) 3 (s) ΔH= -149 kJ/mol
Eqn2 x 3=> 3H2 (g) + 3/2O2 (g) → 3H2O (g) ΔH= -724.8 kJ/mol
Eqn3=> 2Al (s) + 3/2O2 (g) → Al2O3 (s) ΔH= -1676 kJ/mol
211
2Al (s) + 3H2 (g) + 3O2 (g) → 2Al (OH) 3 (s) ΔH= -2549.8 kJ/mol
Al (OH) 3 (s) → Al (s) + 3/2H2 (g) + 3/2O2 (g) ΔH= 1274.9 kJ/mol [216]
4.22 Sodium Hydride, NaH
Energy required to decompose NaH [217] is demonstrated using Hess’s Law
Eqn1 4H2 (g) + 2O2 (g) → 4H2O (l) ΔH= -1144 kJ
Eqn2 2NaO2 (s) → 2Na (s) + 2O2 (g) ΔH= 274 kJ
Eqn3 2NaO2 (s) + 5H2 (g) → 2NaH (s) + 4H2O (l) ΔH= -1026 kJ
Eqn3=> 2NaO2 (s) + 5H2 (g) → 2NaH (s) + 4H2O (l) ΔH= -1026 kJ
Reverse Eqn2=>2Na (s) + 2O2 (g) → 2NaO2 (s) ΔH= -274 kJ
Reverse Eqn1=> 4H2O (l) → 4H2 (g) + 2O2 (g) ΔH= 1144 kJ
2Na (s) + H2 (g) → 2NaH (s) ΔH= -156 kJ
NaH (s) → Na (s) + 1/2H2 (g) ΔH= 78 kJ/mol [217]
4.23 Sodium Hydride, NaH
Energy required to decompose NaH [218] is demonstrated using Hess’s Law
Eqn1 SbH3 (s) + 3NaOH (s) → Sb (OH) 3 (s) + 3NaH (aq) ΔH= -22.8 kJ
Eqn2 3H2 (g) + 2Sb (s) → 2SbH3 (s) ΔH= -655 kJ
Eqn3 Sb (OH) 3 (s) + 3Na (s) → Sb (s) + 3NaOH (s) ΔH= 32.6 kJ
Reverse Eqn1 x 2 =>6NaH (aq) + 2Sb (OH) 3 (s) → 6NaOH (s) + 2SbH3 (s) ΔH= 45.6 kJ
Reverse Eqn3 x 2=>6NaOH (s) + 2Sb (s) → 6Na (s) + 2Sb (OH) 3 (s) ΔH= -65.2 kJ
Reverse Eqn2=> 2SbH3 (s) → 3H2 (g) + 2Sb (s) ΔH= 655 kJ
212
6NaH (aq) → 6Na (s) + 3H2 (g) ΔH= 635.4 kJ
NaH (aq) → Na (s) + 1/2H2 (g) ΔH= 105.9 kJ/mol [218]
4.24 Potassium Hydroxide, KOH
Energy required to decompose KOH [214] is demonstrated using Hess’s Law
Eqn1 KOH (aq) + HCl (aq) → KCl (aq) + H2O (l) ΔH= -57.3 kJ/mol
Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -286 kJ/mol
Eqn3 1/2H2 (g) + 1/2Cl2 (g) +aq → HCl (aq) ΔH= -164 kJ/mol
Eqn4 KCl (s) + aq → KCl (aq) ΔH= 18 kJ/mol
Eqn5 K (s) + 1/2Cl2 (g) + aq → KCl (s) ΔH= -440.3 kJ/mol
Reverse Eqn1=>KCl (aq) + H2O (l) → KOH (aq) + HCl (aq) ΔH= 57.3 kJ/mol
Reverse Eqn3=>HCl (aq) → 1/2H2 (g) + 1/2Cl2 (g) +aq ΔH= 164 kJ/mol
Eqn2=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -286 kJ/mol
Eqn4=> KCl (s) + aq → KCl (aq) ΔH= 18 kJ/mol
Eqn5=> K (s) + 1/2Cl2 (g) + aq → KCl (s) ΔH= -440.3 kJ/mol
1/2H2 (g) + 1/2O2 (g) + K (s) → KOH (aq) ΔH= -487 kJ/mol
KOH (aq) → 1/2H2 (g) + 1/2O2 (g) + K (s) ΔH= 487 kJ/mol [214]
4.25 Lithium Hydroxide, LiOH
Energy required to decompose LiOH [201] is demonstrated using Hess’s Law
Eqn1 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -286 kJ
Eqn2 1/2H2 (g) + 1/2Cl2 (g) → HCl (g) ΔH= -92.33 kJ
Eqn3 LiOH (aq) + HCl (aq) → LiCl (aq) + H2O (l) ΔH= 760.83 kJ
213
Eqn4 LiOH (aq) → LiOH (s) ΔH= 19 kJ
Eqn5 LiCl (s) → LiCl (aq) ΔH= -36 kJ
Eqn6 Li (s) + 1/2Cl2 (g) → LiCl (s) ΔH= 407.5 kJ
Eqn7 HCl (aq) → HCl (g) ΔH= 75 kJ
Reverse Eqn4=> LiOH (s) → LiOH (aq) ΔH= -19 kJ
Eqn3=> LiOH (aq) + HCl (aq) → LiCl (aq) + H2O (l) ΔH= 760.83 kJ
Reverse Eqn7=> HCl (g) → HCl (aq) ΔH= -75 kJ
Eqn2=> 1/2H2 (g) + 1/2Cl2 (g) → HCl (g) ΔH= -92.33 kJ
Reverse Eqn5=> LiCl (aq) → LiCl (s) ΔH= 36 kJ
Reverse Eqn6=> LiCl (s) → Li (s) + 1/2Cl2 (g) ΔH= -407.5 kJ
Reverse Eqn1=> H2O (l) → H2 (g) + 1/2O2 (g) ΔH= 286 kJ
LiOH (s) → 1/2H2 (g) + 1/2O2 (g) + Li (s) ΔH= 485 kJ/mol [201]
4.26 Magnesium Hydroxide, Mg (OH) 2
Energy required to decompose Mg (OH) 2 [219] is demonstrated using Hess’s Law
Eqn1 2Mg (s) + O2 (g) → 2MgO (s) ΔH= -1203.6 kJ
Eqn2 Mg (OH) 2 (s) → MgO (s) + H2O (l) ΔH= 37.1 kJ
Eqn3 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -571.7 kJ
Reverse Eqn2 x 2 => 2MgO (s) + 2H2O (l) → 2Mg (OH) 2 (s) ΔH= -74.2 kJ
Eqn1=> 2Mg (s) + O2 (g) → 2MgO (s) ΔH= -1203.6 kJ
Eqn3=> 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -571.7 kJ
2Mg (s) + 2H2 (g) + 2O2 (g) → 2Mg (OH) 2 (s) ΔH= -1849.5 kJ
Mg (s) + H2 (g) + O2 (g) → Mg (OH) 2 (s) ΔH= -924.75 kJ/mol
214
Mg (OH) 2 (s) → Mg (s) + H2 (g) + O2 (g) ΔH= 924.75 kJ/mol [219]
4.27 Sodium Hydroxide, NaOH
Energy required to decompose NaOH [201,220,214]] is demonstrated using Hess’s Law
Eqn1 NaOH (aq) + HCl (aq) → H2O (l) + NaCl (aq) ΔH= -57.3 kJ/mol
Eqn2 H2O (l) → H2 (g) + 1/2O2 (g) ΔH= 285.8 kJ/mol
Eqn3 1/2H2 (g) + 1/2Cl2 (g) → HCl (g) ΔH= -92.3 kJ/mol
Eqn4 HCl (g) → HCl (aq) ΔH= -75 kJ/mol
Eqn6 NaCl (aq) → NaCl (s) ΔH= -25.2 kJ/mol
Eqn7 NaOH (s) → NaOH (aq) ΔH= -43.22 kJ/mol
Eqn8 Na (s) + 1/2Cl2 (g) →NaCl (s) ΔH= -433.15 kJ/mol
Reverse Eqn7=> NaOH (aq) → NaOH (s) ΔH= 43.22 kJ/mol
Reverse Eqn1=> H2O (l) + NaCl (aq) → NaOH (aq) + HCl (aq) ΔH= 57.3 kJ/mol
Reverse Eqn6=> NaCl (s) → NaCl (aq) ΔH= 25.2 kJ/mol
Eqn8=> Na (s) + 1/2Cl2 (g) →NaCl (s) ΔH= -433.15 kJ/mol
Reverse Eqn4=> HCl (aq) → HCl (g) ΔH= 75 kJ/mol
Reverse Eqn3=> HCl (g) → 1/2H2 (g) + 1/2Cl2 (g) ΔH= 92.3 kJ/mol
Reverse Eqn2=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Na (s) + 1/2H2 (g) + 1/2O2 (g) → NaOH (s) ΔH= -425.13 kJ/mol
NaOH (s) → Na (s) + 1/2H2 (g) + 1/2O2 (g) ΔH= 425.13 kJ/mol [201,220,214]
215
4.28 Ethanol, C2H5OH
Energy required to decompose C2H5OH [221, 214] is demonstrated using Hess’s Law
Eqn1 C2H5OH (l) + 3O2 (g) → 2CO2 (g) + 3H2O (l) ΔH= -1371 kJ/mol
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Reverse Eqn1=>2CO2 (g) + 3H2O (l) → C2H5OH (l) + 3O2 (g) ΔH= 1371 kJ/mol
Eqn2=> 2C (s) + 2O2 (g) → 2CO2 (g) ΔH= -789.02 kJ/mol
Eqn3 x 3=> 3H2 (g) + 3/2O2 (g) → 3H2O (l) ΔH= -857.4 kJ/mol
3H2 (g) + 2C (s) + 1/2O2 (g) → C2H5OH (l) ΔH= -275.42 kJ/mol
C2H5OH (l) → 3H2 (g) + 2C (s) + 1/2O2 (g) ΔH= 275.42 kJ/mol [221, 214]
4.29 Methanol, CH3OH
Energy required to decompose CH3OH [222] is demonstrated using Hess’s Law
Eqn1 CH3OH (l) + 3/2O2 (g) → CO2 (g) + 2H2O (l) ΔH= -726 kJ/mol
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Reverse Eqn1=>CO2 (g) + 2H2O (l) → CH3OH (l) + 3/2O2 (g) ΔH= 726 kJ/mol
Eqn2=> C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol
Eqn3 x 2=> 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -571.6 kJ/mol
2H2 (g) + C (s) + 1/2O2 (g) → CH3OH (l) ΔH= -240 kJ/mol
CH3OH (l) → 2H2 (g) + C (s) + 1/2O2 (g) ΔH= 240 kJ/mol [222]
216
4.30 Propanol, C3H7OH
Energy required to decompose C3H7OH [223] is demonstrated using Hess’s Law
Eqn1 C3H7OH (l) + 9/2O2 (g) → 3CO2 (g) + 4H2O (l) ΔH= -2008 kJ
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Reverse Eqn1=>3CO2 (g) + 4H2O (l) → C3H7OH (l) + 9/2O2 (g) ΔH= 2008 kJ
Eqn2 x 3=> 3C (s) + 3O2 (g) → 3CO2 (g) ΔH= -1183.53 kJ/mol
Eqn3 x 4=> 4H2 (g) + 2O2 (g) → 4H2O (l) ΔH= -1143.2 kJ/mol
3C (s) + 4H2 (g) + 1/2O2 (g) → C3H7OH (l) ΔH= -318.73 kJ/mol
C3H7OH (l) → 3C (s) + 4H2 (g) + 1/2O2 (g) ΔH= 318.73 kJ/mol [223]
4.31 Tetrachloroethylene, C2Cl4
Energy required to decompose C2Cl4 [224,225,226] is demonstrated using Hess’s Law
Eqn1 C2H2 (g) + 3Cl2 (g) → C2Cl4 (g) + 2HCl (g) ΔH= -422.1 kJ
Eqn2 1/2H2 (g) + 1/2Cl2 (g) → HCl (g) ΔH= -92.33 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Eqn5 C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol
Eqn6 C2H2 (g) + 5/2O2 (g) → 2CO2 (g) + H2O (l) ΔH= -1299.5 kJ
Eqn1=> C2H2 (g) + 3Cl2 (g) → C2Cl4 (g) + 2HCl (g) ΔH= -422.1 kJ
Reverse Eqn2 x 2=> 2HCl (g) → H2 (g) + Cl2 (g) ΔH= 184.66 kJ
Reverse Eqn6=> 2CO2 (g) + H2O (l) → C2H2 (g) + 5/2O2 (g) ΔH= 1299.5 kJ
Eqn3=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Eqn5 x 2=> 2C (s) + 2O2 (g) → 2CO2 (g) ΔH= -787.02 kJ/mol
217
2C (s) + 2Cl2 (g) → C2Cl4 (g) ΔH= -10.76 kJ/mol
C2Cl4 (g) → 2C (s) + 2Cl2 (g) ΔH= 10.76 kJ/mol [224,225,226]
4.32 Toulene, C7H8
Energy required to decompose C7H8 [227, 223] is demonstrated using Hess’s Law
Eqn1 C7H8 (l) + 9O2 (g) → 7CO2 (g) + 4H2O (l) ΔH= -3945.9 kJ
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Eqn1=> C7H8 (l) + 9O2 (g) → 7CO2 (g) + 4H2O (l) ΔH= -3945.9 kJ
Reverse Eqn2 x 7=> 7CO2 (g) → 7C (s) + 7O2 (g) ΔH= 2754.57 kJ
Reverse Eqn3 x 4=> 4H2O (l) → 4H2 (g) + 2O2 (g) ΔH= 1143.2 kJ
C7H8 (l) → 7C (s) + 4H2 (g) ΔH= -48.13 kJ/mol [227, 223]
4.33 Chloroform, CHCl3
Energy required to decompose CHCl3 [228] is demonstrated using Hess’s Law
Eqn1 1/2H2 (g) + 1/2Cl2 (g) → HCl (g) ΔH= -92.30 kJ/mol
Eqn2 C (s) + 2H2 (g) → CH4 (g) ΔH= -74.87 kJ/mol
Eqn3 CHCl3 (l) + 3HCl (g) → CH4 (g) + 3Cl2 (g) ΔH= 336.5 kJ
Eqn3=> CHCl3 (l) + 3HCl (g) → CH4 (g) + 3Cl2 (g) ΔH= 336.5 kJ
Eqn1 x 3=> 3/2H2 (g) + 3/2Cl2 (g) → 3HCl (g) ΔH= -276.9 kJ
Reverse Eqn2=>CH4 (g) → C (s) + 2H2 (g) ΔH= 74.87 kJ/mol
218
CHCl3 (l) → C (s) + 1/2H2 (g) + 3/2Cl2 (g) ΔH= 134.47 kJ/mol [228]
4.34 Benzene, C6H6
Energy required to decompose C6H6 [229] is demonstrated using Hess’s Law
Eqn1 C6H6 (l) + 15/2O2 (g) → 6CO2 (g) + 3H2O (l) ΔH= -3169.4 kJ
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Eqn1=> C6H6 (l) + 15/2O2 (g) → 6CO2 (g) + 3H2O (l) ΔH= -3169.4 kJ
Reverse Eqn2 x 6=> 6CO2 (g) → 6C (s) + 6O2 (g) ΔH= 2361 kJ
Reverse Eqn3 x 3=> 3H2O (l) → 3H2 (g) + 3/2O2 (g) ΔH= 857.4 kJ
C6H6 (l) → 6C (s) + 3H2 (g) ΔH= 49 kJ/mol [229]
4.35 Acetone, C3H6O
Energy required to decompose C3H6O [230] is demonstrated using Hess’s Law
Eqn1 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol
Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.83 kJ/mol
Eqn3 C3H6O (l) + 4O2 (g) → 3CO2 (g) + 3H2O (l) ΔH= -1789.9 kJ/mol
Eqn3=> C3H6O (l) + 4O2 (g) → 3CO2 (g) + 3H2O (l) ΔH= -1789.9 kJ/mol
Reverse Eqn1 x 3=>3CO2 (g) → 3C (s) + 3O2 (g) ΔH= 1180.53 kJ
Reverse Eqn2 x 3=>3H2O (l) → 3H2 (g) + 3/2O2 (g) ΔH= 857.49 kJ
C3H6O (l) → 3C (s) + 3H2 (g) + 1/2O2 (g) ΔH=248.12 kJ/mol [230]
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4.36 Methyl tert-butyl ether, C5H12O
Energy required to decompose C5H12O [231,214] is demonstrated using Hess’s Law
Eqn1 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol
Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.83 kJ/mol
Eqn3 C5H12O (l) + 15/2O2 (g) → 5CO2 (g) + 6H2O (l) ΔH= -3368.93 kJ/mol
Eqn3=> C5H12O (l) + 15/2O2 (g) → 5CO2 (g) + 6H2O (l) ΔH= -3368.93 kJ/mol
Reverse Eqn2 x 6=> 6H2O (l) → 6H2 (g) + 3O 2(g) ΔH= 1714.98 kJ
Reverse Eqn1 x 5=> 5CO2 (g) → 5C (s) + 5O2 (g) ΔH= 1967.55 kJ
C5H12O (l) → 5C (s) + 6H2 (g) + 1/2O2 (g) ΔH= 313.6 kJ/mol [231,214]
4.37 Propylene carbonate, C4H6O3
Energy required to decompose C4H6O3 [230,232] is demonstrated using Hess’s Law
Eqn1 C4H6O3 (l) + 4O2 (g) → 4CO2 (g) + 3H2O (l) ΔH= -1807.1 kJ
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.83 kJ/mol
Eqn1=> C4H6O3 (l) + 4O2 (g) → 4CO2 (g) + 3H2O (l) ΔH= -1807.1 kJ
Reverse Eqn2 x 4=> 4CO2 (g) → 4C (s) + 4O2 (g) ΔH= 1574.04 kJ
Reverse Eqn3 x 3=> 3H2O (l) → 3H2 (g) + 3/2O2 (g) ΔH= 857.4 kJ
C4H6O3 (l) → 4C(s) + 3H2 (g) + 3/2O2 (g) ΔH= 624.34 kJ/mol [230,232]
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4.38 Methylene Chloride, CH2Cl2
Energy required to decompose CH2Cl2 [233] is demonstrated using Hess’s Law
Eqn1 CH4 (g) + 2Cl2 (g) → CH2Cl2 (g) + 2HCl (g) ΔH= -202 kJ
Eqn2 C (s) + 2H2 (g) → CH4 (g) ΔH= -74.5 kJ
Eqn3 H2 (g) + Cl2 (g) → 2HCl (g) ΔH= -185 kJ
Eqn1=> CH4 (g) + 2Cl2 (g) → CH2Cl2 (g) + 2HCl (g) ΔH= -202 kJ
Eqn2=> C (s) + 2H2 (g) → CH4 (g) ΔH= -74.5 kJ
Reverse Eqn3=>2HCl (g) → H2 (g) + Cl2 (g) ΔH= 185 kJ
C (s) + H2 (g) + Cl2 (g) → CH2Cl2 (g) ΔH= -91.5 kJ/mol
CH2Cl2 (g) → C (s) + H2 (g) + Cl2 (g) ΔH= 91.5 kJ/mol [233]
4.39 n-heptane, C7H16
Energy required to decompose C7H16 [234] is demonstrated using Hess’s Law
Eqn1 C7H16 (l) + 11O2 (g) → 7CO2 (g) + 8H2O (l) ΔH= -4850 kJ
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Eqn1=> C7H16 (l) + 11O2 (g) → 7CO2 (g) + 8H2O (l) ΔH= -4850 kJ
Reverse Eqn2 x 7=> 7CO2 (g) → 7C (s) + 7O2 (g) ΔH= 2754.57 kJ
Reverse Eqn3 x 8=> 8H2O (l) → 8H2 (g) + 4O2 (g) ΔH= 2286.4 kJ
C7H16 (l) → 7C (s) + 8H2 (g) ΔH= 190.97 kJ/mol [234]
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4.40 Isopropanol, C3H8O
Energy required to decompose C3H8O [235] is demonstrated using Hess’s Law
Eqn1 C3H8O (l) + 9/2O2 (g) → 3CO2 (g) + 4H2O (l) ΔH= -2020 kJ
Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ
Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol
Eqn1=> C3H8O (l) + 9/2O2 (g) → 3CO2 (g) + 4H2O (l) ΔH= -2020 kJ
Reverse Eqn2 x 3=> 3CO2 (g) → 3C (s) + 3O2 (g) ΔH= 1180.53 kJ
Reverse Eqn3 x 4=> 4H2O (l) → 4H2 (g) + 2O2 (g) ΔH= 1143.2 kJ
C3H8O (l) → 3C (s) + 4H2 (g) + 1/2O2 (g) ΔH= 303.73 kJ/mol [235]