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1. Corona discharge method

This is the most common type of ozone generator for most industrial and personal uses. While variations of the “hot spark” coronal discharge method of ozone production exist, including medical grade and industrial grade ozone generators, these units usually work by means of a corona discharge tube.[111] They are typically cost-effective and do not require an oxygen source other than the ambient air to produce ozone concentrations of 3–6%. Fluctuations in ambient air, due to weather or other environmental conditions, cause variability in ozone production. However, they also produce nitrogen oxides as a by-product. Use of an air dryer can reduce or eliminate nitric acid formation by removing water vapor and increase ozone production. At room temperature, Nitric Acid will form into a Vapour that is hazardous if inhaled. Symptoms can include chest pain, shortness of breath, headaches and a dry nose and throat causing a burning sensation.[112] Use of an oxygen concentrator can further increase the ozone production and further reduce the risk of nitric acid formation by removing not only the water vapor, but also the bulk of the nitrogen.

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2. Ultraviolet light

UV ozone generators, or vacuum-ultraviolet (VUV) ozone generators, employ a light source that generates a narrow-band ultraviolet light, a subset of that produced by the Sun. The Sun’s UV sustains the ozone layer in the stratosphere of Earth.

UV ozone generators use ambient air for ozone production, no air prep systems are used (air dryer or oxygen concentrator), therefore these generators tend to be less expensive. However, UV ozone generators usually produce ozone with a concentration of about 0.5% or lower which limits the potential ozone production rate. Another disadvantage of this method is that it requires the ambient air (oxygen) to be exposed to the UV source for a longer amount of time, and any gas that is not exposed to the UV source will not be treated. This makes UV generators impractical for use in situations that deal with rapidly moving air or water streams (in-duct air sterilization, for example). Production of ozone is one of the potential dangers of ultraviolet germicidal irradiation. VUV ozone generators are used in swimming pools and spa applications ranging to millions of gallons of water. VUV ozone generators, unlike corona discharge generators, do not produce harmful nitrogen by-products and also unlike corona discharge systems, VUV ozone generators work extremely well in humid air environments. There is also not normally a need for expensive off-gas mechanisms, and no need for air driers or oxygen concentrators which require extra costs and maintenance.

3. Cold Plasma

In the cold plasma method, pure oxygen gas is exposed to a plasma created by dielectric barrier discharge. The diatomic oxygen is split into single atoms, which then recombine in triplets to form ozone.

Cold plasma machines utilize pure oxygen as the input source and produce a maximum concentration of about 5% ozone. They produce far greater quantities of ozone in a given space of time compared to ultraviolet production. However, because cold plasma ozone generators are very expensive, they are found less frequently than the previous two types.

The discharges manifest as filamentary transfer of electrons (micro discharges) in a gap between two electrodes. In order to evenly distribute the micro discharges, a dielectric insulator must be used to separate the metallic electrodes and to prevent arcing.

Some cold plasma units also have the capability of producing short-lived allotropes of oxygen which include O4, O5, O6, O7, etc. These species are even more reactive than ordinary O3

4. Electrolytic

Electrolytic ozone generation (EOG) splits water molecules into H2, O2, and O3. In most EOG methods, the hydrogen gas will be removed to leave oxygen and ozone as the only reaction products. Therefore, EOG can achieve higher dissolution in water without other competing gases found in corona discharge method, such as nitrogen gases present in ambient air. This method of generation can achieve concentrations of 20–30% and is independent of air quality because water is used as the source material. Production of ozone electrolytically is typically unfavorable because of the high overpotential required to produce ozone as compared to oxygen. This is why ozone is not produced during typical water electrolysis. However, it is possible to increase the overpotential of oxygen by careful catalyst selection such that ozone is preferentially produced under electrolysis. Catalysts typically chosen for this approach are lead dioxide[115] or boron-doped diamond.[116]

The ozone to oxygen ratio is improved by increasing current density at the anode, cooling the electrolyte around the anode close to 0 °C, using an acidic electrolyte (such as dilute sulfuric acid) instead of a basic solution, and by applying pulsed current instead of DC.[11

5. Special Considerations

  • Ozone cannot be stored and transported like other industrial gases (because it quickly decays into diatomic oxygen) and must therefore be produced on site. Available ozone generators vary in the arrangement and design of the high-voltage electrodes. At production capacities higher than 20 kg per hour, a gas/water tube heat-exchanger may be utilized as ground electrode and assembled with tubular high-voltage electrodes on the gas-side. The regime of typical gas pressures is around 2 bars (200 kPa) absolute in oxygen and 3 bars (300 kPa) absolute in air. Several megawatts of electrical power may be installed in large facilities, applied as one phase AC current at 50 to 8000 Hz and peak voltages between 3,000 and 20,000 volts. Applied voltage is usually inversely related to the applied frequency.

    The dominating parameter influencing ozone generation efficiency is the gas temperature, which is controlled by cooling water temperature and/or gas velocity. The cooler the water, the better the ozone synthesis. The lower the gas velocity, the higher the concentration (but the lower the net ozone produced). At typical industrial conditions, almost 90% of the effective power is dissipated as heat and needs to be removed by a sufficient cooling water flow.

    Because of the high reactivity of ozone, only few materials may be used like stainless steel (quality 316L), titanium, aluminium (as long as no moisture is present), glass, polytetrafluorethylene, or polyvinylidene fluoride. Viton may be used with the restriction of constant mechanical forces and absence of humidity (humidity limitations apply depending on the formulation). Hypalon may be used with the restriction that no water comes in contact with it, except for normal atmospheric levels. Embrittlement or shrinkage is the common mode of failure of elastomers with exposure to ozone. Ozone cracking is the common mode of failure of elastomer seals like O-rings.

    Silicone rubbers are usually adequate for use as gaskets in ozone concentrations below 1 wt%, such as in equipment for accelerated aging of rubber samples.

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