Ozone

 

Introduction

Ozone is used in water treatment for disinfection and oxidation. Early application of ozone in the United States was primarily for non-disinfection purposes such as color removal or taste and odor control. However, since the implementation of the SWTR and proposal of the DBP rule, ozone usage for primary disinfection has increased in the United States.

 

 

Ozone Chemistry

Ozone exists as a gas at room temperature. The gas is colorless with a pungent odor readily detectable at concentrations as low as 0.02 to 0.05 ppm (by volume), which is below concentrations of health concern. Ozone gas is highly corrosive and toxic. Ozone is a powerful oxidant, second only to the hydroxyl free radical, among chemicals typically used in water treatment. Therefore, it is capable of oxidizing many organic and inorganic compounds in water. These reactions with organic and inorganic compounds cause an ozone demand in the water treated, which should be satisfied during water ozonation prior to developing a measurable residual.

Ozone is sparingly soluble in water. At 20oC, the solubility of 100 percent ozone is only 570 mg/L. While ozone is more soluble than oxygen, chlorine is 12 times more soluble than ozone. Ozone concentrations used in water treatment are typically below 14 percent, which limits the mass transfer driving force of gaseous ozone into the water. Consequently, typical concentrations of ozone found during water treatment range from <0.1 to 1mg/L, although higher concentrations can be attained under optimum conditions.

Basic chemistry research has shown that ozone decomposes spontaneously during water treatment by a complex mechanism that involves the generation of hydroxyl free radicals. The hydroxyl free radicals are among the most reactive oxidizing agents in water.

The spontaneous decomposition of ozone occurs through a series of steps. The exact mechanism and reactions associated have not been established, but mechanistic models have been proposed. It is believed that hydroxyl radicals forms as one of the intermediate products, and can react directly with compounds in the water. The decomposition of ozone in pure water proceeds with hydroxyl free radicals produced as an intermediate product of ozone decomposition, resulting in the net production of 1.5 mole hydroxyl free radicals per mole ozone.

In the presence of many compounds commonly encountered in water treatment, ozone decomposition forms hydroxyl free radicals. Ozone demands are associated with the following:

 

 

 

Ozone Generation

Because ozone is an unstable molecule, it should be generated at the point of application for use in water treatment. It is generally formed by, combining an oxygen atom with an oxygen molecule (O2):  This reaction is endothermic and requires a considerable input of energy.

Schönbein first discovered synthetic ozone through the electrolysis of sulfuric acid. Ozone can be produced several ways, although one method, corona discharge, predominates in the ozone generation industry. Ozone can also be produced by irradiating an oxygen-containing gas with ultraviolet light, electrolytic reaction and other emerging technologies.

Corona discharge, also known as silent electrical discharge, consists of passing an oxygen-containing gas through two electrodes separated by a dielectric and a discharge gap. Voltage is applied to the electrodes, causing an electron flowthrough across the discharge gap. These electrons provide the energy to disassociate the oxygen molecules, leading to the formation of ozone. Figure 3-3 shows a basic ozone generator.

 

 

Figure 3-3. Basic Ozone Generator

 

 


System Components

As shown in Figure 3-4, ozone water treatment systems have four basic components: a gas feed system, an ozone generator, an ozone contactor, and an off-gas destruction system. The gas feed system provides a clean, dry source of oxygen to the generator. The ozone contactor transfers the ozone-rich gas into the water to be treated, and provides contact time for disinfection (or other reactions). The final process step, off-gas destruction, is required as ozone is toxic in the concentrations present in the off-gas. Some plants include an off-gas recycle system that returns the ozone-rich off-gas to the first contact chamber to reduce the ozone demand in the subsequent chambers. Some systems also include a quench chamber to remove ozone residual in solution.

 

 

Gas Feed Systems

Ozone feed systems are classified as using air, high purity oxygen or mixture of the two. High purity oxygen can be purchased and stored as a liquid (LOX), or it can be generated on-site through either a cryogenic process, with vacuum swing adsorption (VSA), or with pressure swing adsorption (PSA). Cryogenic generation of oxygen is a complicated process and is feasible only in large systems. Pressure swing adsorption is a process whereby a special molecular sieve is used under pressure to selectively remove nitrogen, carbon dioxide, water vapor, and hydrocarbons from air, producing an oxygen rich (80–95 percent O2) feed gas. The components used in pressure swing adsorption systems are similar to high pressure air feed systems in that both use pressure swing molecular absorption equipment. Low pressure air feed systems use a heat reactivated desiccant dryer.

Oxygen Feed Systems - Liquid oxygen feed systems are relatively simple, consisting of a storage tank or tanks, evaporators to convert the liquid to a gas, filters to remove impurities, and pressure regulators to limit the gas pressure to the ozone generators.

Air Feed Systems - Air feed systems for ozone generators are fairly complicated as the air should be properly conditioned to prevent damage to the generator. Air should be clean and dry, with a maximum dew point of -60º C (-80º F) and free of contaminants. Air preparation systems typically consist of air compressors, filters, dryers, and pressure regulators. Figure 3-5 is a schematic of large scale air preparation system.

Particles greater than 1 mm and oil droplets greater than 0.05 mm should be removed by filtration (Langlais et al., 1991). If hydrocarbons are present in the feed gas, granular activated carbon filters should follow the particulate and oil filters. Moisture removal can be achieved by either compression or cooling (for large-scale system), which lowers the holding capacity of the air, and by desiccant drying, which strips the moisture from the air with a special medium. Desiccant dryers are required for all air preparation systems. Large or small particles and moisture cause arcing which damages generator dielectrics.

Typically, desiccant dryers are supplied with dual towers to allow regeneration of the saturated tower while the other is in service. Moisture is removed from the dryer by either an external heat source or by passing a fraction (10 to 30 percent) of the dried air through the saturated tower at reduced pressure. Formerly, small systems that require only intermittent use of ozone , a single desiccant tower is sufficient, provided that it is sized for regeneration during ozone decomposition time.

Air preparation systems can be classified by the operating pressure: ambient, low (less than 30 psig), medium, and high (greater than 60 psig) pressure. The distinguishing feature between low and high pressure systems is that high pressure systems can use a heatless dryer. A heatless dryer operates normally in the 100 psig range, rather than the 60 psig range. Rotary lobe, centrifugal, rotary screw, liquid ring, vane, and reciprocating compressors can be used in air preparation systems.

Reciprocating and liquid ring compressors are the most common type used in the United States, particularly in small systems, the former because the technology is so prevalent and the latter because liquid ring compressors do not need aftercoolers. Air receivers are commonly used to provide variable air flow from constant volume compressors. Oil-less compressors are used in modern systems to avoid hydrocarbons in the feed gas

 

 

 

Ozone Generators

The voltage required to produce ozone by corona discharge is proportional to the pressure of the source gas in the generator and the width of the discharge gap. Theoretically, the highest yield (ozone produced per unit area of dielectric) would result from a high voltage, a high frequency, a large dielectric constant, and a thin dielectric. However, there are practical limitations to these parameters. As the voltage increases, the electrodes and dielectric materials are more subject to failure. Operating at higher frequencies produces higher concentrations of ozone and more heat requiring increased cooling to prevent ozone decomposition. Thin dielectrics are more susceptible to puncturing during maintenance. The design of any commercial generator requires a balance of ozone yield with operational reliability and reduced maintenance.

Two different geometric configurations for the electrodes are used in commercial ozone generators: concentric cylinders and parallel plates. The parallel plate configuration is commonly used in small generators and can be air cooled. The glass dielectric/high voltage electrode in commercial generators resembles a fluorescent light bulb and is commonly referred to as a “generator tube.”

Most of the electrical energy input to an ozone generator (about 85 percent) is lost as heat. Because of the adverse impact of temperature on the production of ozone, adequate cooling should be provided to maintain generator efficiency. Excess heat is removed usually by water flowing around the stainless steel ground electrodes. The tubes are arranged in either a horizontal or vertical configuration in a stainless steel shell, with cooling water circulating through the shell.

Ozone generators are classified by the frequency of the power applied to the electrodes. Low frequency (50 or 60 Hz) and medium frequency (60 to 1,000 Hz) generators are the most common found in the water industry, however some high frequency generators are available. Medium frequency generators are efficient and can produce ozone economically at high concentrations, but they generate more heat than low frequency generators and require a more complicated power supply to step up the frequency supplied by utility power. New installations tend to use medium or high frequency generators.

 

 

Ozone Contactors

Once ozone gas is transferred into water, the dissolved ozone reacts with the organic and inorganic constituents, including any pathogens. Ozone not transferred into the process water during contacting is released from the contactor as off-gas. Transfer efficiencies of greater than 80 percent typically are required for efficient ozone disinfection.

Common ozone dissolution methods include:

 

 

Bubble Diffuser Contactors

The bubble diffuser contactor is commonly used for ozone contacting in the United States and throughout the world. This method offers the advantages of no additional energy requirements, high ozone transfer rates, process flexibility, operational simplicity, and no moving parts. Figure 3-7 illustrates a typical three stage ozone bubble diffuser contactor. This illustration shows a countercurrent flow configuration (ozone and water flowing in opposite directions), an alternating cocurrent/countercurrent arrangement, and a cocurrent flow configuration (ozone and water flowing in the same direction). Also, the number of stages can vary from two to six for ozone disinfection, with the majority of plants using two or three chambers for contacting and reaction.

Bubble diffuser contactors are typically constructed with 18 to 22 ft water depths to achieve 85 to 95 percent ozone transfer efficiency. Since all the ozone is not transferred into the water, the contactor chambers are covered to contain the off-gas. Off-gas is routed to an ozone destruct unit, usually catalysts, thermal, or thermal/catalysts.

 

 

Bubble diffuser contactors use ceramic or stainless steel diffusers that are either rod-type or disc-type to generate bubbles. Design considerations for these diffusers (Renner et al., 1988) include:

The configuration of the bubble diffuser contactor structure should best be designed to provide plug flow hydraulics. This configuration will minimize the overall volume of the contactor while still meeting the CT requirements for the system. Contactor volume is determined in conjunction with the applied ozone dosage and estimated residual ozone concentration to satisfy the disinfection CT requirement. Table 3-4 summarizes the advantages and disadvantages of the bubble diffuser contactor. Also, diffuser pore clogging can be a problem when ozone dosages are intermittent and/ or when iron and manganese oxidation is required. Channeling of bubbles is dependent on the type of diffusers used and the spacing between diffusers.

 

 

 


Injector Dissolution

The injector contacting method is commonly used in Europe, Canada, and the United States. Ozone is injected into a water stream under negative pressure, which is generated in a venturi section, pulling the ozone into the water stream. In many cases, a sidestream of the total flow is pumped to a higher pressure to increase the available vacuum for ozone injection. After the ozone is injected into this sidestream, the sidestream containing all the added ozone is combined with the remainder of the plant flow under high turbulence to enhance dispersion of ozone into the water. Figure 3-8 illustrates typical in-line and sidestream ozone injection systems.

 

 


The gas to liquid ratio is a key parameter used in the design of injector contacting systems. This ratio should be less than 0.067 cfm/gpm to optimize ozone transfer efficiency. Meeting this criterion typically requires relatively low ozone dosages and ozone gas concentrations greater than 6 percent by weight. High concentration ozone gas can be generated using a medium frequency generator and/or liquid oxygen as the feed gas. To meet the CT disinfection requirements, additional contact time is required after the injector, typically in a plug flow reactor. The additional contact volume is determined in conjunction with the applied ozone dosage and estimated residual ozone concentration to satisfy the disinfection CT requirement.

Table 3-5 summarizes the advantages and disadvantages of injection contacting.

 

 



Turbine Mixer Contactors

Turbine mixers are used to feed ozone gas into a contactor and mix the ozone with the water in the contactor. Figure 3-9 illustrates a typical turbine contactor. The illustrated turbine mixer design shows the motor located outside the basin, allowing for maintenance access. Other designs use a submerged turbine.

Ozone transfer efficiency for turbine mixers can be in excess of 90 percent. However, the power required to achieve this efficiency is 2.2 to 2.7 kW-hr of energy per lb of ozone transferred.

Turbine mixing basins vary in water depth from 6 to 15 ft, and dispersion areas vary from 5 to 15 ft. Again, as with injector contacting, sufficient contact time may not be available in the turbine basin to meet disinfection CT requirements; consequently additional contact volume may be required.

 



Table 3-6 summarizes advantages and disadvantages for the turbine mixer contactor.

 

 

 


Off-gas Destruction Systems

The concentration of ozone in the off-gas from a contactor is usually well above the fatal concentration. For example, at 90 percent transfer efficiency, a 3 percent ozone feed stream will still contain 3,000 ppm of ozone in the off-gas. Off-gas is collected and the ozone converted back to oxygen prior to release to the atmosphere. Ozone is readily destroyed at high temperature (> 350° C or by a catalyst operating above 100° C) to prevent moisture buildup. The off-gas destruct unit is designed to reduce the concentration to 0.1 ppm of ozone by volume, the current limit set by OSHA for worker exposure in an eight hour shift. A blower is used on the discharge side of the destruct unit to pull the air from the contactor, placing the contactor under a slight vacuum to ensure that no ozone escapes.

 

 

Instrumentation

Instrumentation should be provided for ozone systems to protect both personnel and the equipment. Gas phase ozone detectors should be provided in spaces such as generator rooms where ozone gas may be and personnel are routinely present. An ozone detector is also needed on the outlet from the off-gas destruct unit to ensure the unit is working properly. These units should be interlocked with the ozone generator controls to shut down the ozone generation system should excess ozone be detected. A dew point detector on the feed gas supply just upstream of an ozone generator is required to protect the generator from moisture in the feed gas (when air is the feed gas). Flow switches on the cooling water supply are needed to protect the generator from overheating and a pressure switch to prevent over pressurization.

Other instrumentation can be used to monitor and control the ozone process, although manual control is adequate for small systems, but most small systems are designed to operate automatically, particularly in remote areas. Ozone monitors can be used in conjunction with process flow meters to match ozone dose to process demands and control ozone generation. Sophisticated control schemes can be implemented to minimize the cost of dosing with ozone and reduce operator attention requirements. Many systems include residual monitoring at various points in the contactor to maintain desired ozone residual and prevent energy-wasting overdosing.

 

 

Operation and Maintenance

Even though ozone systems are complex, using highly technical instruments, the process is highly automated and very reliable, requiring only a modest degree of operator skill and time to operate an ozone system. Maintenance on generators requires skilled technicians. If trained maintenance staff are not available at the plant, this work can be done by the equipment manufacturer. Some facilities, such as the 600 mgd Los Angeles Aqueduct Filtration Plant, use plant mechanics to perform generator and facilities maintenance. Therefore, backup units are usually installed. Generators should be checked daily when in operation. After a shutdown, dry air or oxygen should be allowed to flow through the generator to ensure that any moisture has been purged prior to energizing the electrodes. At initial start up and after long down times, this process may take up to 12 hours and usually longer when air is the feed gas. As an alternative, a small flow of dry air can be passed through the generator continuously when it is in standby mode to maintain the dry condition.

Filters and desiccant in air preparation systems should be changed periodically, with the frequency depending on the quality of the inlet air and the number of hours in operation. Compressors require periodic service, depending on the type and operating time. LOX tanks should be periodically pressure tested. Piping and contact chambers should be inspected periodically to check for leaks and corrosion.

Dielectric tubes should be periodically cleaned. This operation should be performed when the generator efficiency drops 10-15 percent. Cleaning the tubes is a delicate operation as the tubes are fragile and expensive. Adequate space should be provided for the cleaning operation and for storage of spare tubes.

 

 

Primary Uses and Points of Application of Ozone

Primary Uses of Ozone

Ozone is used in drinking water treatment for a variety of purposes including:

 

 

Disinfection

Ozone is a powerful oxidant able to achieve disinfection with less contact time and concentration than all weaker disinfectants, such as chlorine, chlorine dioxide, and monochloramine. However, ozone can only be used as a primary disinfectant since it cannot maintain a residual in the distribution system. Thus, ozone disinfection should be coupled with a secondary disinfectant, such as chlorine, chloramine, or chlorine dioxide for a complete disinfection system.

 

 

Iron and Manganese Oxidation

Ozone will oxidize iron and manganese, converting ferrous (2+) iron into the ferric (3+) state and 2+ manganese to the 4+ state. The oxidized forms will precipitate as ferric hydroxide and manganese hydroxide. The precise chemical composition of the precipitate will depend on the nature of the water, temperature, and pH. The ozone dose required for oxidation is 0.43 mg/mg iron and 0.88 mg/mg manganese. Iron oxidizes at a pH of 6-9 but manganese is more effective at a pH of around 8. Also, over-ozonation has no effect on iron, but will resolubilize manganese, which then should be reduced to manganese dioxide downstream.

 

 

Oxidation of Taste and Odor Compounds

Ozone is used to oxidize/destroy taste and odor-causing compounds because many of these compounds are very resistant to oxidation. Ozone is an effective oxidant for use in taste and odor treatment. They found ozone doses of 2.5 to 2.7 mg/L and 10 minutes of contact time (ozone residual of 0.2 mg/L) significantly reduced taste and odors in the specific waters they tested. Most early U.S. water plants (i.e., 1940-1986) installed ozonation specifically for taste and odor removal.

 

 

DBP Precursor Control

Early work on oxidation of DBP precursors seemed to indicate that the effects of ozonation, prior to chlorination, were quite site-specific and unpredictable. The key variables that seem to determine ozone’s effect are dose, pH, alkalinity, and, above all, the nature of the organic material. At low pH levels, precursor destruction by ozone is quite effective; however, above some critical pH, ozone actually is less effective and in fact sometimes increases the amount of chlorination byproduct precursors. For most humic substances this critical pH is 7.5, which is the approximate level at which decomposition of ozone to hydroxyl free radicals increases rapidly, thus increasing organic oxidation rates. Therefore, the implications that at lower pH (approximately 6-7), at which molecular ozone predominates over the hydroxyl free radical, the initial THM precursor byproducts are different in nature than those formed by the hydroxyl free radicals oxidized at higher pH levels. This is logical in light of the greater oxidation potential of the hydroxyl free radical over that of ozone.

As alkalinity increases, it has a beneficial effect on THM formation potential (THMFP). This is because alkalinity scavenges any hydroxyl free radicals formed during ozonation, leaving molecular ozone as the sole oxidant, which is only capable of oxidizing organic precursors to a lower oxidation sequence than does the hydroxyl free radical. Given neutral pH and moderate levels of bicarbonate alkalinity, THMFP level reductions of 3 to 20 percent have been shown at ozone doses ranging from 0.2 to 1.6 mg ozone per mg carbon.

 

 

Increase Organic Biodegradation

Ozone can be effective in partially oxidizing organics in the water to biodegradable compounds that can be removed by biological filtration (Demers and Renner, 1992). This partial oxidation gives rise to lower molecular weight organics that are more easily biodegradable. This increase in the biodegradable fraction of organic carbon occurs as a result of moderate to high levels of ozonation. These ozone levels are typical of the doses commonly applied for disinfection.

 

 

Coagulation and Filtration Improvement

Ozone has been reported by some to improve coagulation and filtration efficiency.
However, others have found no improvement in filter effluent turbidity due to ozonation collected data from a large water treatment plant showing that pre-ozonation was more effective than pre-chlorination to reduce filter effluent turbidities. The cause of the improved coagulation is not clear, but several possibilities have been offered, including:

 

 

Points of Application

The typical locations for feeding ozone in a water treatment plant are at the head of the treatment plant (raw water) pre-ozonation and after sedimentation. Raw water quality and turbidity and ozone demand (the amount of ozone required for all oxidation requirements of the water) can be used to assess how to use ozone in the treatment process. Table 3-7 lists the criteria for selecting ozone feed points based on these two parameters. By moving the ozonation process further downstream after sedimentation, the ozone demand and production of byproducts are reduced. The advantage of placing ozone ahead of filtration is that biodegradable organics produced during ozonation can be removed by subsequent biological activity in the filters.

 

 

 


Impact on Other Treatment Processes

Ozonation does have an impact on other processes at the water treatment facility. The impacts of ozone addition include the following:

 

 

Disinfection Parameters

The rate of decomposition of ozone is a complex function of temperature, pH, and concentration of organic solutes and inorganic constituents. The following sections describe the effects that pH, temperature, and suspended matter have on the reaction rate of ozone and pathogen inactivation.

The ability to maintain a high aqueous ozone concentration is critical from a regulatory disinfection compliance standpoint. This means that factors that accelerate ozone decomposition are undesirable for inactivation because the ozone residual dissipates faster and therefore reduces the CT credit, requiring a corresponding increase in the ozone applied, thus increasing cost.

 

 

pH

Studies have indicated that pH has little effect on the ability of dissolved ozone residuals to inactivate acid-fast bacteria, such as Mycobacteria and Actinomycetes. A slight decrease has been found in the virucidal efficacy of ozone residuals as pH decreased.  Changes in disinfection efficacy with variations in pH appear to be caused by the ozone decomposition rate. Ozone decomposition occurs faster in higher-pH aqueous solutions and forms various types of oxidants with differing reactivities. Tests carried out at constant ozone residual concentration and different pH values showed that the degree of microorganism inactivation remained virtually unchanged. More recent studies have indicated decreased virus inactivation by ozone at alkaline pH (pH 8 to 9) for poliovirus 1.

Inactivation of Giardia muris cysts was found to improve when the pH increased from 7 to 9. This phenomenon was attributed to the possible changes in cyst chemistry making it easier for ozone to react with the cyst constituents at the higher pH levels. However, the same study found that inactivation of Naegleria gruberi cysts was slower at a pH 9 than at lower pH levels, thereby indicating that pH effects are organism-specific.

 

 

Temperature

As temperature increases, ozone becomes less soluble and less stable in water; however, the disinfection and chemical oxidation rates remain relatively stable. Studies haveshown that although increasing the temperature from 0 to 30oC can significantly reduce the solubilityof ozone and increases its decomposition rate, temperature has virtually no effect on the disinfectionrate of bacteria. In other words, the disinfection rate was found to be relativelyindependent of temperature at typical water treatment plant operating temperatures despite thereduction in solubility and stability at higher temperatures.

 

 

Suspended Matter

Ozone inactivation of viruses and bacteria contained in aluminum floc (in the size range comparable to those that could typically escape filtration) was not reduced at floc turbidity levels of 1 and 5 NTU. This study demonstrated that the microorganisms received no protection from the aluminum floc. Similar results have been obtained for poliovirus 1, coxsackie virus A9, and E. coli associated with bentonite clay (Boyce et al., 1981). However, adsorption of the f2 bacteriophage at 1 and 5 NTU of bentonite clay was found to retard the rate of inactivation of ozone.

In some instances, river waters heavily polluted with organic matter were ozonated, and the results indicated a degradation of large organic molecules into fragments more easily metabolized by microorganisms. This fragmentation coupled with the inability of ozone to maintain an active concentration in the distribution system, has led to increased slime growth and, consequently, water quality deterioration during distribution.

 

 

Status of Analytical Methods

During operation of an ozonation system it is necessary to analyze for ozone in both the liquid and gas phase to determine the applied ozone dose, ozone transfer efficiency and (for primary disinfection) residual ozone level. The gas stream exiting the ozone generator is monitored for ozone content to determine the applied ozone dose. The off-gas exiting the ozone contactor is monitored to determine the amount of ozone transferred to the liquid phase in the contactor and to calculate the ozone transfer efficiency. The disinfected water exiting the ozone contactor is monitored for residual ozone to ensure that CT values are met.

In addition, the ambient air in any ozone generating or handling room and ozone destruct off-gas are monitored for ozone concentration to protect workers in the event of leakages or destruct system failure.

 

 

Monitoring of Gas Phase Ozone

Points in an ozone treatment system where gas-phase ozone is monitored include:

The range of ozone concentrations to be measured in the gas phase varies from less than 0.1 ppm by volume (0.2 mg/m3 NTP) in ambient air and ozone destruct off-gas, to 1 to 2 percent (10 g/m3 NTP) in contactor off-gas, to as high as 15 percent by weight (200 g/m3 NTP) in the ozone generator output.

Analytical methods for monitoring gas-phase ozone include:

 

 

Summary

Advantages and Disadvantages of Ozone Use

The following list highlights selected advantages and disadvantages of using ozone as a disinfection method for drinking water (Masschelein, 1992). Because of the wide variation of system size, water quality, and dosages applied, some of these advantages and disadvantages may not apply to a particular system.

 

 

Advantages

 

 

Disadvantages