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.     

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     

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.     

Iron and Manganese Removal with Ozonation in the Presence of Humic Substances

The conditions for the removal of iron and manganese contained in slightly mineralized water, rich in humic substances, were determined in a case where an intermediate oxidation was provided in a conventional potabilization line comprising a coagulationflocculation stage with iron salts.

The experiments were conducted both on a synthetic water, with or without addition of humic substances, and on raw water from the Moulin-Papon dam. While iron was easily removed by simply increasing the pH measurement from 8.2 to 8.5 without intermediate oxidation, ozonation applied to water with a pH of nearly 8.4 did not enable the manganese to be removed with a low ozone dose (about 1 mg/L) unless a significant amount of bicarbonates (120 to 130 mg/L as CaCO₃) were injected prior to the ozonation-filtration stage.

As it removes the manganese from the water, intermediate ozonation also removes the abatement of organics on the filters, and lowers the THM buildup potential.     

A RELATIONSHIP BETWEEN CHEMICAL STRUCTURE AND THE CRITICAL TEMPERATURE

Six distillation column models have been used in studies of the usefulness of the Inverse Nyquist Array (INA) method for design of dual composition control for distillation. Five of the column models are experimental, one describing an industrial column, the others four pilot plants. One column model is obtained by modeling from first principles.

The control strategies investigated and compared are multiloop SISO, 2-way decoupling and l-way decoupling. The control variables are the standard ones, i.e. reflux flow and boilup.

In most of the cases INA has been found to be a useful tool for design of the loops and for comparison of the different control approaches. INA has also been found to be useful for simultaneous tuning of the decouplers and the feedback controllers.

For 2-way decoupling the criterion to minimize interaction at the critical frequency for each primary feedback loop has been found useful in most, but not all, cases. The scheme can be designed by pure gains in the decouplers and there is no reason to introduce dynamics into the decouplers—the systems studied are already sufficiently rich in dynamics.

INA has been found to be a suitable vehicle for the choice between the two possible l-way decoupling schemes.

With the design approach taken, l-way decoupling has been found to provide considerably better control quality than 2-way decoupling in two of the six systems, the differences in control quality being small in the other cases.

The effect of model mismatching on the results, caused e.g. by process nonlinearities, is discussed and simple rules to decrease the parameter sensitivity for 2-way decoupling schemes are given. When model mismatching is considered, the advantage of l-way decoupling over 2-way decoupling seems to increase.

One deficiency of the INA design as used in this paper is that it does not single out the design which is to be preferred on the grounds of robustness.     

Advantages of Preozonation in the Upgrading of the Mont Valérien Plant in France

The Mont Valérien plant supplies water to the western suburbs of Paris. Raw water comes from the River Seine downstream from the city. The old plant comprised two treatment lines: a slow sand filtration line built 80 years ago and a rapid settling and filtration line built in 1960. The process for the upgraded plant was determined after an in-depth study including industrial-scale experiments and laboratory tests.

The new treatment line includes the following: preozonation, oagulationflocculation and settling in a sludge-blanket type settling tank (PULSATOR), rapid gravity sand filtration, ozonation, and granular activated carbon filtration.

Results from laboratory tests used for the design are presented: ozonation rate, advantages for the quality of the treated water, expected reagejit savings, etc.     

Effect of Preozonation on Flux and Water Quality in Ozonation-Ultrafiltration Hybrid System for Water Treatment

The effect of ozonation on membrane flux and water quality was investigated in an ozonation ultrafiltration (UF) hybrid system. Crossflow UF was performed in total recycle mode to study the effect of ozonation on membrane fouling and disinfection by-product formation potentials of organics. Total organic carbon (TOC), UV absorbance at 254 ran (UV254) and trihalomethane formation potential (THMFP) were measured as water quality parameters.

The effect of ozonation on membrane flux was found to be largely dependent on raw water quality as well as ozone dose. In case of upstream water (A), preozonation achieved significant flux enhancement regardless of ozone dose. Whereas, for the downstream water (B), the steady state flux was increased or decreased depending on ozone dose.

The analysis based on the resistance-in-series model provided the mechanistic interpretation on the membrane flux variation. Ozonation in an ozone-ultrafiltration system always brought about a decrease in cake resistance (R_c) and an increase in fouling resistance (Rf). Based on the measurement of particle size distribution and zeta potential, the reduction in cake resistance through ozonation was attributed to an increase in particle size due to “ozone-induced particle destabilization”. However, the increase in the fouling resistance seems to be caused partly by the microbial characteristics of raw water.

Although there was little effect on TOC, ozone-UF treatment could get much higher removal of UV 254, THMFP (lday) and THMPF/TOC ratio than UF treatment alone.     

Modeling of nonstationary processes during separation of multicomponent isotope mixtures

The article presents a mathematical model for calculation of nonstationary hydraulic and separation processes in a gas centrifuge (GC) cascade for separation of multicomponent isotope mixtures. The model has been applied to calculate the parameters of nonstationary processes in a GC cascade for separation of krypton, germanium and tungsten isotopes. As a result, the specifics of the excess holdup distribution along the cascade stages has been identified, and variations of the isotope concentrations in a nonstationary process have been revealed. The data obtained show that the proposed mathematical model is able to adequately describe nonstationary hydraulic processes in GC cascades for separation of multicomponent isotope mixtures.

Highlights:

Mathematical model of cascade for separation of multicomponent isotope mixture has been developed.

The model verification has been done.

The isotope transient regularities into cascade during nonstationary processes has been identified.     

What is New in Performance Plastics?

The field of performance plastics is showing remarkable vitality and growth, even though the participants find the price to be high in terms of technical and sales support required, together with high capital investment for plants.

There has been a high degree of proliferation of new products in the form of new polymers, new grades of existing polymers, as well as filled, reinforced, alloyed versions. While this does introduce new degrees of freedom in material selection, it is a source of significant confusion for the design engineers who have to cope with selecting the preferred material from among the many that are available. The choices and data bases are becoming confusing.

Various forms of relatively exotic, aromatic-monomer chemistry are being applied, but the emphasis appears to be on new amorphous polymers.

High-performance requirements exist in virtually all segments of the plastics field; the major end uses are in aerospace, automotive, business machines, electrical/electronics, food packaging, and medical applications.

Foreign presence has strongly increased as European companies have increased imports or have purchased established product lines or business units.

There will be continued pressure on the performance plastics from the lower priced materials which are countering with upgraded, modified, alloyed versions of their own. There is also increased competition between thermoplastics and thermosets as the result of material developments and process refinements.     

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.     

Bromate Surveys in French Drinking Waterworks

Two bromate surveys were made recently in order to evaluate the frequency of bromate appearance in drinking waters issued from waterworks including one or two ozonation steps. The First survey was carried out on 47 waterworks. Two sampling campaigns were analyzed in cool and warm seasons. The objective of the second survey was to follow, during 4 to 10 months, at 12 selected waterworks.

The aim of this paper is to present the data obtained and to try to model for some waterworks the bromate formation by means of some important parameters (Br, O₃/DOC, T° and pH) of water to ozonate.

The main conclusion is that the bromate presence in distributed drinking waters is a reality for waterworks using ozonation steps, especially in warm period of the year. In the case of some waterworks, disinfection by sodium hypochlorite increased bromate levels in distributed water.

As shown by others on a laboratory-scale level, a multi-linear regression allows us the prediction of the bromate formation from some determining parameters, for some waterworks. However, the poor values of the linear regression lead us to have some doubts about its universal application in the real situation of an operating waterworks. A better evaluation of “C.t” will be required in the future in order to get a better prediction by the use of multi linear regression.     

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.     

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.

     

Reactivity Studies In The Ozonolysis Of Pollutants Using A Perforated Spinning Disc Reactor To Enhance Mass Transfer

A perforated spinning disc ozone contactor is described with reference to its use as an absorber with simultaneous chemical reaction.

Greatly enhanced mass transfer coefficients k_L are measured whilst simultaneously maintaining low ozone loss. Comparisons of k_L and volumetric coefficient, k_L a values, are made with more conventional packed or bubble columns.

Acetic acid, 2-propanol and 4-nitrophenol, representing a wide reactivity range, are used to elucidate the applicability of rotating contactors in effluent treatment. It has been possible to study the effects of surface activity on mass transfer with subsequent reaction and to generate design data for the next generation of rotating contactors.     

MECHANISM OF CLASSIFICATION IN A STURTEVANT-TYPE AIR CLASSIFIER

The estimation of air velocity distributions and particle trajectories is inevitable to analyse the mechanism of classification, but the direct measurement of il is extremely difficult.

The authors, here report three dimensional air velocity distributions within the inside drum of model Sturtevant-type air classifier measured by a spherical five-holed Pitot-lube, and also two dimensional particle ejecting velocities on a model distributor determined by photography.

Using those results, the cut size calculated from particle trajectories in the classifier is compared with the experimental results and theoretical values.     

Quinoxaline Ozonation in Aqueous Solution

The oxidation of quinoxaline by ozone in aqueous solution is investigated. The chemical and kinetic evolution of the oxidation process at varying pH are followed by means of semi-batch and batch ozonation experiments. Results indicate that quinoxaline ozonation can develop according to both radical and ionic mechanisms whose relative occurrence can be varied by means of addition to the reacting system of radical scavengers or ozone decomposition promoters. It is shown that each mechanism involves an initial attack of ozone to both the homocyclic and heterocyclic rings of quinoxaline. Pyrazinedicarboxylic acid is formed as a stable final product in ionic ozonation, whereas it appears as an intermediate still reactive towards ozone in radical ozonation. Despite this, the radical ozonation of quinoxaline appears to be more selective than ionic zonation with respect to production of pyrazinedicarboxylic acid. Reaction schemes are proposed to account for the observed kinetic behaviors and product formations.

Oxidation experiments have also been extended to pyrazine, and its sensitivity to only radical ozonation is shown.     

EFFECT OF CONTAMINANTS ON CRITICAL HEAT FLUX AT LOW PRESSURES

Critical heat flux (CHF) tests were performed to evaluate the effect of dissolved, nonreactive contaminants on low-pressure industrial boilers. These tests were conducted on a 2.38-inch (60.5 mm) I.D. vertical smooth bore tube with nonuniform circumferential heating at pressures between 100 and 500 psia (0.69 and 3.45 MPa). Tests were performed under two water chemistry conditions: clean (less than 1.6 ppm total dissolved solids) and contaminated (greater than 2000 ppm TDS). With all other operating parameters held constant, the following effects of contamination on the steam quality (X) at CHF were determined at the pressures indicated:

At 100 psia (0.69 MPa) X_clean < X_cont

At 300 psia (2.1 MPa) X_clean?X_cont

At 500 psia (3.5 MPa) X_clean > X_cont

The effect of contamination on CHF was found to be a function of pressure, initial contaminant concentration, and the relative steam quality at which CHF conditions occur. These results are compared to data available in the open literature where X_clean is always greater than X_cont. A method for correlating these data is also illustrated.