The Photochemical Generation of Ozone : Present State–of–the–Art

This paper reflects an investigation of the feasibility of photochemical generation of ozone by irradiating gases containing oxygen with Hg lamps of the highest performance emitting the 185 nm line. Besides the expected photostationary equilibrium, determining factors for practical yields in ozone generation by the 185 nm wavelength are : the reactor and gas temperature, the reactor geometry, and the gas composition, as well as the pressure.

Further developments are expected in the field of lamp construction and also improvement of reactor geometry. A better knowledge of the aging of the lamps is required, as well as of the photochemical reactions of oxygen in the technologies applied.

Systems presently available are most promising for application on small scale or in areas of public water distribution which have no developed structure.

     

Hydroxyl Radical Oxidation Processes For The Removal Of Triazine From Natural Water

The purpose of this study was to point out processes that can provide triazine oxidation via hydroxyl radical production in a water treatment line. We focus our attention on:

- oxido-flocculation, using Fe²⁺, H₂O₂

- inter-oxidation, using O₃, H₂O₂ and eventually an heterogeneous catalyst.

- disinfection, using UV, O₃ and H₂O₂ combinations.

Results show that triazines can be removed by all these processes with different efficiencies. At full scale, the O₃/H₂O₂ process presents the best performances from an economical and technical point of view.     

First Year Operation Report of the Corona Discharge Ozone Swimming Pool Water Treatment Systems at the Peck Aquatic Facility,Milwaukee, Wisconsin

The two corona discharge ozone swimming pool water treatment systems installed in the Peck Aquatic Center in Milwaukee, WI now have been in continuous operation since September, 1987. The two pools are part of the Karl Jewish Campus Facility of the Harold and Judy Sampson Campus of the Milwaukee Jewish Community Center.

The operation of these water treatment systems has shown that safe and high quality pool water is obtained reliably and economically. One pool (Main Pool) is of Olympic size, the other (Learner pool) is designed especially for use by children. Both pools utilize a full corona discharge ozone water treatment system. They were the first ozone systems in the U.S. to be built for public pools using the process of ozonation, flocculation, filtration, ozone removal and residual chlorination.

An extensive testing program was initiated in cooperation with the Wisconsin Department of Health. The bacteriological water quality from these swimming pools was in compliance with Wisconsin State Health Regulations and the German DIN Standard 19,643.

The first year of operation of the Peck Aquatic Center has shown that the corona discharge ozone pool water treatment process can:

1) Operate reliably in a public swimming pool environment without the need for highly or special operator qualifications.

2) Produce continuously bacteria- and virus-free pool water without the harmful and unpleasant effects of chlorine.

3) Creates a user constituency group praising and promoting the use of “minimal chlorine swimming” in the community.     

Biological Filtration for Ozone and Chlorine DBP Removal

This paper presents results from a water treatment pilot testing program in Winnipeg, Canada (pop. 650,000) which evaluated a DAF/ozone/deep bed filtration process. As part of the testing program, biological filtration using GAC and anthracite media was assessed for the removal of ozone DBPs and background chlorine DBPs (due to upstream chlorination of the source water). The results were used to evaluate the effectiveness of biological filtration for DBP removal.

High filtration rates were tested in this study. The 2.1m deep filters were run at a hydraulic loading rate (HLR) of 35 m/h with an empty bed contact time (EBCT) of only 3.6 minutes.

The important findings of this work are

?The high-rate biologically active carbon (BAC) filters met the objective of controlling ozone DBPs. These results confirm that high rate, low EBCT filters can provide significant biodegradation. Anthracite biofilters provided significantly less removal of ozone DBPs.

?The high rate BAC filters showed significant reduction of background HAAs. BAC reduced the background HAAs to below the long-term target of 30 μg/L. Anthracite biofilters did not exhibit HAA removal.

?Biological filtration with either media was ineffective for background THM removal. The long-term target of 40 μg/L could not be achieved without GAC adsorption.     

Comparative Efficiency Of Three Systems (O3, O3/H2O2, and O3/TiO2) For The Oxidation Of Natural Organic Matter In Water

CATAZONE is a new process of heterogeneous catalytic ozonation in which water is ozonated in the presence of a solid catalyst composed of titanium dioxide. The efficiency of this O₃/TiO₂ system has been compared to the two well-known oxidant systems: ozone alone and ozone combined with hydrogen peroxide.

This comparison was undertaken on three models of natural organic compounds : an aquatic fulvic acid, a protein and a disaccharide. The first results showed the following order of relative efficiency: O₃/TiO₂ > O₃/H₂O₂ > O₃ as far as Total Organic Carbon (TOC) removal was concerned.     

Removal of Aromatic Nitro Compounds from Water by Ozonation

Experimental studies were carried out on the removal of five species of aromatic nitro hydrocarbons by ozonation. Ultraviolet spectrograms with distinct absorption peaks were plotted for each of them. It has been found that the absorbances of aqueous solutions containing the single compounds mentioned above increase to different extents at the wave lengths ranging from 200 to 230 nanometers with increase of ozone dosages. This is ascribed to the nitrite ions splitting out of the benzene rings and being further oxidized to nitrate ions by ozonation.

It has been indicated that the removal of the five species of aromatic nitro compounds by ozonation can well be expressed mathematically by first order reaction equations. Besides, the reaction constants and half-life periods for various species of the tested nitro compounds were calculated at different temperatures and pH.

An ozonation effect index (OI) was developed in the study to express the degree of degradation of substrates by ozonation, by means of which the five aromatic nitro hydrocarbons were compared with each other and finally ranked in the following order from greatest to smallest degrees of degradation:

p-nitroaniline > nitrobenzene > p-dinitrobenzene > p-nitrotoluene > m-dinitrobenzene

It has also found that the CODm/M ratio increases with ozone doses. This means that some easily degradable intermediates are produced, and increase in concentration with increase of ozone dose in the ozonation process.

The mechanisms of removing the five aromatic nitro hydrocarbons are discussed from the viewpoint of orienting effects of substituent groups on the aromatic rings.     

New Pilot Plant Studies at the Budapest Waterworks

The quality of water provided by the Budapest Waterworks should comply with the standards prescribed by the European Community. According to these provisions, on one of the major water-producing regions (Csepel Island), rows of wells of 60,000 m³/day yield have been closed recently, and in the immediate future further plants would have been closed because of the high iron and manganese content of the water.

The raw water obtained from 100 different wells will be purified by a water treatment plant of 150,000 m³/day capacity. Considering the high iron content (0.05–0.15 mg/L) and manganese content (0.05–0.2 mg/L), the raw water fails to comply with the requirements of the potable water standard.

Since 1990, over a period of three years, we conducted water purification experiments in several stages. In these, three methods of oxidizing as well as single and double layer open rapid filters were applied to oxidize the manganese (and, to a lesser extent, the water) present in dissolved form, resp., to destroy various living organisms.

In the course of the experiments, it became clear that the chlorine and chlorine + air methods are efficient in case of a small quantity of iron to be oxidized and only 20–25% of the dissolved manganese content could be oxidized.

Neither of the two methods could ensure firm management of microbiological and bacteriological characteristics. The best results were obtained by ozone oxidation, in which case the chemical oxidizing process was almost fully completed and even the chlorine-resistant living organisms could be destroyed.

On the basis of the experiments carried out, the investment program of the water treatment plant was worked out and the conditions of an international tender were compiled whose winner will be commissioned to build up the water works in the time period 1993–1996. One of the main steps of the proposed technology is the ozone treatment.     

The Oxidation of Manganese and Disinfection By Ozonation in Water Purification Processing

The surface water of a river has been used as the raw water by the Waterworks Bureau of Osaka City. At present, the manganese contained in the raw water is oxidized by breakpoint chlorination and all oxides are removed by coagulation, sedimentation followed by rapid sand filtration, with chlorine being used as the final disinfectant.

Prechlorination was not conducted in the ongoing pilotplant experiment of an advanced water purification process with ozone and granular activated carbon. It is necessary, therefore, to oxidize manganese by the oxidative effect of ozone instead of prechlorination.

It is important for the treatment of manganese to adjust the ozone dosage because manganese is oxidized up to the soluble septavalent state by the surplus ozone. Since ozone does not continue to exist for very long in water, though its disinfecting power is high, final disinfection by chlorine is required.     

Recent Advances in Flame Retardancy of Polymeric Materials (Materials,Applications, Industry Developments,Markets)

The Fifth Annual Conference on Flame Retardancy was held May 24–26, 1994, at the Ramada Plaza Hotel, Stamford, Connecticut, USA. The conference was organized by Business Communications Company, Inc., Norwalk, Connecticut (Company President, Mr. Louis Naturman; Conference Coordinator, Mrs. Sharon D. Faust). New materials (polymers, blends, composites), their applications, industry developments, and markets were considered. Specifically, the most important topics were:

Introduction of new technological achievements and development in the field of flame retardancy (FR)

Review of the current state of science and technology in FR

Review of applications and markets for FR products

Presentation of recent developments in local and global standardization and in testing technology

Discussion of toxicity and environmental issues

Provision of a unique opportunity for newcomers to FR research technology and marketing to become acquainted with the FR field in all its aspects

Discussion of halogen-based and non-halogen-based flame retardant chemicals, syngergism, intumescence, FR mechanisms, modeling, flame parameters, inherently FR polymers, and polymer blends     

Controlling Blown Polyethylene Film Optical Properties

The conventional blown process imparts an inherent haze to the product. The percentage of haze varies with certain process variables:

1. Surface irregularities caused by melt flow phenomena

2. Crystallization behavior

3. Melt drawing phenomena in certain types of polyethylene     

Use Of Static Mixer For Oxidation And Disinfection By Ozone

Ozone is used in drinking water treatment as a biocide, as an oxidant and as a pretreatment in order to improve the performance of subsequent processes. Increasing concern over the quality of drinking water has led to a number of new stringent regulations in the control of chemical and microbiological contaminants. Disinfection deals with the concept of “CT”, which is the need to maintain a certain minimum concentration for a given time. Under ideal laboratory conditions, it is 0.4 mg O₃/L for 4 min. In practice, since the method for the CT determination has not been finalized by the EPA, “T” can be the minimum detention time of 90% of total flow, and “C” can be a measured ozone residual at the outlet of cells of the contactor. New standards for micropollutants in drinking water imply an optimization of the ozonation step, by improving the ozone transfer from gas to water, and the control of the detention time as well as ozone residual within the contactor.

All these considerations have led us to use static mixers to transfer ozone into water. This process enables us to control the ozone concentration in water and detention time. It is a very simple system, with very low maintenance requirements due to the lack of moving parts. Civil engineering is minimized. A pilot scale study is presented here. It took place at the Méry-sur-Oise water treatment plant, on a pilot plant working at 8-12 m³/h. It is composed of a static mixer for the transfer of ozone from gas to liquid, linked to an air lift to separate gas from liquid, providing ozonated water.

The optimization of transfer was achieved by studying the impact of water flow, gas flow and ozone concentration in the gas. It is possible to reach 90% of transfer in less than 15 s. Headloss (ΔP) across the mixer is a function of gas and water flows and remains economically very acceptable as 0.15 bar for 12 m³/h.

Atrazine removal was studied using a static mixer, an air lift and a contact pipe 80-m long, providing an optimum contact time phase, working as a plug flow reactor. Ozone and H₂O₂/O₃ treatments were compared. The maximum reduction of atrazine concentrations (e.g., for an infinite contact time) is a function of the amount of transferred ozone, but H₂O₂ influences the kinetics of the reaction. In the presence of H₂O₂ with a ratio of H₂O₂ to O₃ of 0.4 w/w, maximum elimination is reached in 2 min 30 s.

The effect of such treatments on environmental bacteria also was followed. A counting of total germs at 20°C showed a decrease of 1- to 3-logs 10 after 1 min 30 s of contact time for about 2 mg/L of transferred ozone. No significant difference between treatments with or without H₂O₂ was shown. The same conclusions were obtained from heterotrophic plate counts (37°C) and epifluorescence countings.     

Influence of Temperature on Bacterial Development in Waters

Microbiological stability in water mains has become an increasing problem for waterworks where more and more surface water is used for distribution requirements. Even when surface water is treated, appropriately, it usually contains a higher amount of organic compounds than does groundwater, and during certain periods, can attain temperatures between 20 and 25°C. Furthermore, ozonization applied during treatment modifies structures of the dissolved organic materials.

Twenty bacterial strains capable of aftergrowth were isolated starting from ozonized surface water, from water of subterranean origin, and from a mixture of these two types of water. Six typical strains were used to determine the importance of the temperature factor on aftergrowth in five types of waters of different characteristics.

Three criteria for the evaluation of aftergrowth are: the growth rate factor (r₂), the growth yield (maximum number of germs/mL when growth stops), and the latency time (in hours). The results, in triplicate, obtained from growth curves then were submitted to an analysis of variance by two cross classifications.

It was established that aftergrowth is related to the classical Pseudomonas and Azobacter families, but also to the species of Bacillus, Corynebacter, Micrococcus, Vibrionaceae, and even Enterobacter. Furthermore, it has been proven that the temperature factor is most important in all aspects, as an increase in water temperature enhances all growth characteristics: shortening of the lag-phase; increase in growth-rate factor; and yield.

Under practical conditions, the significant growth delay is very important. With Pseudomonas putida, the lag-phase is on the order of three days at +7.5°C and 10 hours at +17°C.     

Water Disinfection: A Relationship Between Ozone and Aldehyde Production

In the water potabilization plant of Turin city (Italy), the oxidation process is carried out with ozone. Due to its well-known insufficient performance, it is necessary to add alternative oxidants (hypochlorite ion and chlorine dioxide). In this paper, we discuss the formation of linear carbonyl groups during surface water treatment in Turin.

The results obtained in the field confirm the synthesis of some aliphatic carbonyl compounds of low molecular weight. This phenomenon happens preeminently during the ozone disinfection process and, secondarily, during the other disinfection processes.

Experimental results show that, in this last event, chlorine reacts with organic substances, and in a second moment, after organics consumption, if chlorine is still in a sufficient concentration, oxidizing them.     

Immunological Examinations in Patients with Chronic Conditions under Administration of Ozone/Oxygen Mixtures

In four groups of patients with chronic conditions receiving an ozone application (intravascular administration of ozone/oxygen mixtures with or without autohemotherapy), the immunoglobulins IgA, IgG and IgM were determined in serum; in groups 1 and 2, lysozyme and vitamin A values also were measured. The groups were broken down as follows:

Group 1: 19 patients with carcinoma of the cervix. Group 2: 20 patients with carcinoma of the ovaries. Group 3: patients with chronic conditions (80% patients with rheumatoid arthritis), shortterm study (34 patients). Group 4: patients with chronic conditions (80% patients with rheumatoid arthritis), long–term study (47 patients). A further breakdown into statistical categories in groups 1 and 2 showed no significant changes in the immunoglobulins examined, including the vitamin A and lysozyme values.

A short-term influence in group 3 became evident through a significant increase in immunoglobulin G, whereas no significant decrease was observed in all immunoglobulins in group 4. An immunosuppressive effect of the ozone applied could not be detected in any of the 4 groups.     

Pilot-Scale Evaluation Of The Effects Of Mixing On Ozone Disinfection Of Escherichia Coli In A Semi-Batch,Stirred Tank Reactor

A research program was undertaken to examine the effects of mixing intensity and post-ozonation conditions on the survival of Escherichia coli ATCC 11775 in a high quality secondary wastewater effluent with a total organic carbon content of 8 mg/L and a chemical oxygen demand of 26 mg/L. The study was conducted using a pilot-scale, semi-batch stirred tank reactor with a 6-blade Rushton turbine. Two power conditions were investigated: 255 W/m³ and 870 W/m³. Two post-ozonation conditions also were investigated. In the first, a headspaceless sample was withdrawn and stored in the dark, in a quiescent condition. For the second, the gas flow to the reactor was stopped, but mixing was continued.

For equivalent contact times, it was found that two orders of magnitude more E. coli survived under the second post-ozonation condition when compared with the first condition. There was also a significant difference associated with the mixing intensity in the contactor, with the higher power input resulting in less efficient inactivation of E. coli.

The results confirm the importance of designing an ozone contactor to promote the maintenance of aqueous ozone in the contactor. In addition, optimum ozone mass-transfer may require different contacting conditions than those required for optimum disinfection performance. It was concluded that the design of ozone contactors should consider the use of at least two-stages: one optimized for ozone mass-transfer and one optimized for disinfection contacting.     

Economics of Treating Waste Gases from an Air Stripping Tower Using Photochemically Generated Ozone

Air stripping towers have been recommended for the removal of volatile organic compounds (VOCs) in drinking water supply and industrial waste treatment systems. This technique removes VOCs economically in the liquid phase. It can, however, create adverse secondary environmental impacts by removing VOCs from the water and discharging them to the air.

A commonly proposed method for controlling .VOC emissions is filtration of the off-gas through adsorption of the stripped organics in the off-gas by granular activated carbon. The high incremental cost of this alternative has produced an interest in alternative control technologies.

One alternative currently available is based on short wavelength ultraviolet (UV) radiation. This technique combines the effects of ozone generation, free radical formation and photolysis of the contaminants to effectively control the VOC emissions. This technique is known as Advanced Photo Oxidation (APO)^R.

The cost for APO is $0.27/m³ for a 3.8 m³/hr contaminated water system. A system of this size is adequate for a groundwater decontamination project where a moderate length of time is available for restoration of the site. The cost of a conventional air stripping tower with Granular Activated Carbon (GAC) adsorption emissions control in this size range would be $0.40 to $0.45/m³ (J.M. Montgomery, 1986).

Additional testing will be required to fully develop design guidelines for different contaminants and larger systems. Another area for additional technical documentation is the application of this technique to the liquid phase oxidation of VOCs.     

Effects Of Ozone As A Biocide In An Experimental Cooling Water System

Experimental work on a laboratory recirculating apparatus, for the simulation of a cooling water system has yielded information on the effectiveness of ozone as a biocide for biofouling control. Biofilms were developed within glass tubes of the simulated cooling water system using filtered mainswater and Pseudomonas fluorescens as the test bacteria. A summary of the results obtained is presented and an interpretation of these results relating to the full-scale application of ozone is provided.

Ozonated water was produced using a contact system specifically designed for these tests by Ozotech Ltd. Ozone residual concentrations in the order of 0.1 mg/L were found to be capable of removing 80-99% of the biofilm in single applications. However, effectiveness of ozone was dependent on morphology, thickness and age of the biofilms. Intermittent application of ozone, using residual concentrations < 0.1 mg/L, was found to be capable of weakening the biofilm, but a minimum period of 3-h was required for effective control.

The fluid velocity was found to affect the rate and amount of biofilm removed. The effects of fluid velocities in the range 0.5-2.5 m/sec were examined. In general, the higher the velocity the greater the initial rate of removal and the percentage of the biofilm removed; this suggested that ozone action was mass transfer dependent.

The effect of ozone on bacterial cell structure was investigated using scanning electron microscopy techniques. Changes in cell structure were revealed after contact with ozone and residuals above 0.4 mg/L were required for 100% kill of bacterial suspensions.

In conclusion, the effectiveness of ozone for full-scale application will vary depending on the morphology of the biofilm, the velocity of the fluid and the ozone dose applied. An ozone dosing regime for commercial application is suggested.     

MEASUREMENT OF INTERFACIAL AREA AND MASS TRANSFER COEFFICIENTS BY CHEMICAL METHOD OF C02 ABSORPTION INTO AQUEOUS SOLUTIONS OF NaOH IN A MODEL COLUMN WITH EXPANDED METAL SHEET PACKING

The theory of gas absorption accompanied by fast pseudo-fast order reaction which considered dependences of diffusivity, kinetic constant and Henry's law constant on absolute temperature and ionic strength was used to obtain values of effective interfacial areas and mass transfer coefficients in gas and liquid phase.

Experimental measurement of carbon dioxide absorption from mixture with air was performed in a pilot-plant column with expanded metal sheet packing irrigated with sodium hydroxide solution.

Resulting liquid and gas-side mass transfer coefficients are compared with values obtained from physical Absorption measurement of carbon dioxide into water and with measurement of gas-side mass transfer coefficient for sulphur dioxide in the same column.

The differences between determined values are discussed.