Ozone Production
In 1857, von Siemens developed the first industrial ozone generator, which was based on corona discharges. Two
concentrical glass tubes were used; the outer tube was covered externally by a layer of tin, and the inner tube was
covered internally by a layer of tin. Air was circulated through the annular space. This technology was later improved by
the addition of circulating cooling fluids along the discharge air or oxygen gap, resulting in lower generation temperatures
and less thermal destruction of the ozone.
The generation of ozone involves the intermediate formation of atomic oxygen radicals which can react with molecular
oxygen. All processes that can dissociate molecular oxygen into oxygen radicals are potential ozone generation
reactions. Energy sources that make this action possible are electrons or photon quantum energy. Electrons can be used
from high-voltage sources in the silent corona discharge, from nuclear sources, and from electrolytic processes.
Suitable photon quantum energy includes UV light of wavelengths lower than 200 nm and γ-rays.
In nature, ozone generation occurs when oxygen molecules reacts in the presence of electrical discharges, e.g.,
lightning, and by action of high energy electromagnetic radiation. Some electrical equipment inadvertently generates
levels of ozone that can be easily smelled; this is especially true if there is a spark or a very high voltage.
Ozone Generation by Corona Discharge
Corona discharge in a dry process gas containing oxygen is presently the most widely used method of ozone generation
for water treatment. A classical production line is composed of the following units: gas source (compressors or liquefied
gas), dust filters, gas dryers, ozone generators, contacting units, and off gas destruction.
It is of utmost importance that a dry process gas is applied to the corona discharge. Limiting nitric acid formation is also
important in order to protect the generators and to increase the efficiency of the generation process. In normal operation
of properly designed systems, a maximum of 3 to 5 g nitric acid is obtained per kilogram ozone produced with air. If
increased amounts of water vapor are present, larger quantities of nitrogen oxides are formed when spark discharges
occur. Also, hydroxyl radicals are formed that combine with oxygen radicals and also ozone. Both reactions reduce the
ozone generation efficiency. Consequently, the dryness of the process gas is of relevant importance to obtain a yield of
ozone. Moreover, with air, nitrogen oxides can form nitric acid, which can cause corrosion. The presence of organic
impurities in the feed gas should be avoided, including impurities arising from engine exhaust, leakages in cooling
groups, or leakages in electrode cooling systems.
The formation of ozone through electrical discharge in a process gas is based on the non homogeneous corona
discharge in air or oxygen. There are numerous distributed micro discharges by which the ozone is effectively generated.
It appears that each individual micro discharge lasts only several nanoseconds, lasting about 2.5 to 3 times longer in air
than in oxygen. The current density ranges between 100 and 1000 A.cm-2. By using oxygen or enriching the process air
in oxygen, the generating capacity of a given ozone generator can be increased by a factor ranging form 1.7 to 2.5
versus the production capacity with air, depending on the design parameters (for example, gas discharge gap and
current frequency). The nominal design capacity at which operation can be performed on a permanent basis must be
considered to be at least 20 to 30 percent. The yield obtained when using an oxygen-enriched process gas is increased
with a smaller gas space and an increased electrical current frequency. Since all variations result in energy loss in the
form of heat, cooling of the process gas is very important. The most efficient form of cooling is the “both-side” cooling
system, which is a system that has cooling on both the high-voltage side and on the ground side. However, in case of
accidental breakage of the dielectric, the cooling liquid (for example, water) enters the discharge gap and causes short-
circuiting of the entire system. Therefore, cooling only the ground side is the safer design.
The plasma created by the high voltage field between the electrodes (see schematic of an ozone system and photos of
an actual system) in an ozone generator is called a corona and is similar to the effect observed in lightning and static
discharges. Ozone is formed by the following reactions:
A 1/2 O2 = O Heat of Reaction A= +59.1 Kcal
B O + O2 = O3 Heat of Reaction B = -24.6 Kcal
AB 3/2 O2 = O3 Heat of Reaction AB= +34.5 Kcal
The overall reaction (AB) that produces ozone requires energy and is an endothermic reaction that obtains energy from
the electric discharge.
Other methods of ozone generation include:
Photochemical Ozone Generation
The formation of ozone from oxygen exposed to UV light at 140-190 nm was first reported by Lenard in 1900 and fully
assessed by Goldstein in 1903. It was soon recognized that the active wavelengths for technical generation are below
200 nm. In view of present technologies with mercury-based UV-emission lamps, the 254-nm wavelength is transmitted
along with the 185-nm wavelength, and photolysis of ozone is simultaneous with its generation. Moreover, the relative
emission intensity is 5 to 10 times higher at 254 nm compared to the 185-nm wavelength.
Attempts to reach a suitable photo stationary state of ozone formation with mercury lamps have failed. The main reason
for this failure is that thermal decomposition is concomitant with ozone formation. Except for small-scale uses or
synergistic effects, the UV-ozone process (the UV-photochemical generation of ozone) has not reached maturity.
Important phases requiring additional development include the development of new lamp technologies with less aging
and higher emission intensity at wavelengths lower than 200 nm.
Electrolytic Ozone Generation
Electrolytic generation of ozone has historical importance because synthetic ozone was first discovered by Schönbein in
1840 by the electrolysis of sulfuric acid. The simplicity of the equipment can make this process attractive for small-scale
users or users in remote areas.
Many potential advantages are associated with electrolytic generation, including the use of low-voltage DC current, no
feed gas preparation, reduced equipment size, possible generation of ozone at high concentrations, and generation in
the water,eliminating the ozone-to-water contacting processes. Problems and drawbacks of the method include: corrosion
and erosion of the electrodes, thermal overloading due to anodic over-voltage and high current densities, need for
special electrolytes or water with low conductivity, and with the in-site generation process, incrustations and deposits are
formed on the electrodes, and production of free chlorine is inherent to the process when chloride ions are present in the
water or the electrolyte used.
Radiochemical Ozone Generation
High-energy irradiation of oxygen by radioactive rays can promote the formation of ozone. Even with the favorable
thermodynamic yield of the process and the interesting use of waste fission isotopes, the cheminuclear ozone generation
process has not yet become a significant application in water or waste water treatment due to its complicated process
requirements.
In 1857, von Siemens developed the first industrial ozone generator, which was based on corona discharges. Two
concentrical glass tubes were used; the outer tube was covered externally by a layer of tin, and the inner tube was
covered internally by a layer of tin. Air was circulated through the annular space. This technology was later improved by
the addition of circulating cooling fluids along the discharge air or oxygen gap, resulting in lower generation temperatures
and less thermal destruction of the ozone.
The generation of ozone involves the intermediate formation of atomic oxygen radicals which can react with molecular
oxygen. All processes that can dissociate molecular oxygen into oxygen radicals are potential ozone generation
reactions. Energy sources that make this action possible are electrons or photon quantum energy. Electrons can be used
from high-voltage sources in the silent corona discharge, from nuclear sources, and from electrolytic processes.
Suitable photon quantum energy includes UV light of wavelengths lower than 200 nm and γ-rays.
In nature, ozone generation occurs when oxygen molecules reacts in the presence of electrical discharges, e.g.,
lightning, and by action of high energy electromagnetic radiation. Some electrical equipment inadvertently generates
levels of ozone that can be easily smelled; this is especially true if there is a spark or a very high voltage.
Ozone Generation by Corona Discharge
Corona discharge in a dry process gas containing oxygen is presently the most widely used method of ozone generation
for water treatment. A classical production line is composed of the following units: gas source (compressors or liquefied
gas), dust filters, gas dryers, ozone generators, contacting units, and off gas destruction.
It is of utmost importance that a dry process gas is applied to the corona discharge. Limiting nitric acid formation is also
important in order to protect the generators and to increase the efficiency of the generation process. In normal operation
of properly designed systems, a maximum of 3 to 5 g nitric acid is obtained per kilogram ozone produced with air. If
increased amounts of water vapor are present, larger quantities of nitrogen oxides are formed when spark discharges
occur. Also, hydroxyl radicals are formed that combine with oxygen radicals and also ozone. Both reactions reduce the
ozone generation efficiency. Consequently, the dryness of the process gas is of relevant importance to obtain a yield of
ozone. Moreover, with air, nitrogen oxides can form nitric acid, which can cause corrosion. The presence of organic
impurities in the feed gas should be avoided, including impurities arising from engine exhaust, leakages in cooling
groups, or leakages in electrode cooling systems.
The formation of ozone through electrical discharge in a process gas is based on the non homogeneous corona
discharge in air or oxygen. There are numerous distributed micro discharges by which the ozone is effectively generated.
It appears that each individual micro discharge lasts only several nanoseconds, lasting about 2.5 to 3 times longer in air
than in oxygen. The current density ranges between 100 and 1000 A.cm-2. By using oxygen or enriching the process air
in oxygen, the generating capacity of a given ozone generator can be increased by a factor ranging form 1.7 to 2.5
versus the production capacity with air, depending on the design parameters (for example, gas discharge gap and
current frequency). The nominal design capacity at which operation can be performed on a permanent basis must be
considered to be at least 20 to 30 percent. The yield obtained when using an oxygen-enriched process gas is increased
with a smaller gas space and an increased electrical current frequency. Since all variations result in energy loss in the
form of heat, cooling of the process gas is very important. The most efficient form of cooling is the “both-side” cooling
system, which is a system that has cooling on both the high-voltage side and on the ground side. However, in case of
accidental breakage of the dielectric, the cooling liquid (for example, water) enters the discharge gap and causes short-
circuiting of the entire system. Therefore, cooling only the ground side is the safer design.
The plasma created by the high voltage field between the electrodes (see schematic of an ozone system and photos of
an actual system) in an ozone generator is called a corona and is similar to the effect observed in lightning and static
discharges. Ozone is formed by the following reactions:
A 1/2 O2 = O Heat of Reaction A= +59.1 Kcal
B O + O2 = O3 Heat of Reaction B = -24.6 Kcal
AB 3/2 O2 = O3 Heat of Reaction AB= +34.5 Kcal
The overall reaction (AB) that produces ozone requires energy and is an endothermic reaction that obtains energy from
the electric discharge.
Other methods of ozone generation include:
Photochemical Ozone Generation
The formation of ozone from oxygen exposed to UV light at 140-190 nm was first reported by Lenard in 1900 and fully
assessed by Goldstein in 1903. It was soon recognized that the active wavelengths for technical generation are below
200 nm. In view of present technologies with mercury-based UV-emission lamps, the 254-nm wavelength is transmitted
along with the 185-nm wavelength, and photolysis of ozone is simultaneous with its generation. Moreover, the relative
emission intensity is 5 to 10 times higher at 254 nm compared to the 185-nm wavelength.
Attempts to reach a suitable photo stationary state of ozone formation with mercury lamps have failed. The main reason
for this failure is that thermal decomposition is concomitant with ozone formation. Except for small-scale uses or
synergistic effects, the UV-ozone process (the UV-photochemical generation of ozone) has not reached maturity.
Important phases requiring additional development include the development of new lamp technologies with less aging
and higher emission intensity at wavelengths lower than 200 nm.
Electrolytic Ozone Generation
Electrolytic generation of ozone has historical importance because synthetic ozone was first discovered by Schönbein in
1840 by the electrolysis of sulfuric acid. The simplicity of the equipment can make this process attractive for small-scale
users or users in remote areas.
Many potential advantages are associated with electrolytic generation, including the use of low-voltage DC current, no
feed gas preparation, reduced equipment size, possible generation of ozone at high concentrations, and generation in
the water,eliminating the ozone-to-water contacting processes. Problems and drawbacks of the method include: corrosion
and erosion of the electrodes, thermal overloading due to anodic over-voltage and high current densities, need for
special electrolytes or water with low conductivity, and with the in-site generation process, incrustations and deposits are
formed on the electrodes, and production of free chlorine is inherent to the process when chloride ions are present in the
water or the electrolyte used.
Radiochemical Ozone Generation
High-energy irradiation of oxygen by radioactive rays can promote the formation of ozone. Even with the favorable
thermodynamic yield of the process and the interesting use of waste fission isotopes, the cheminuclear ozone generation
process has not yet become a significant application in water or waste water treatment due to its complicated process
requirements.
Spartan Environmental Technologies
Air and Water Treatment
Air and Water Treatment
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Spartan Environmental
Technologies, L.L.C.
7383 Lauren J Dr
Mentor, OH 44060
USA
Phone: 800-492-1252
Fax: 440-368-3569
E-mail: info@
spartanwatertreatment.com
Technologies, L.L.C.
7383 Lauren J Dr
Mentor, OH 44060
USA
Phone: 800-492-1252
Fax: 440-368-3569
E-mail: info@
spartanwatertreatment.com