Kinetic Study of the Ozonation of Some Industrial Wastewaters

Kinetic studies of the ozonation of two wastewaters released by distillery and tomato processing plants have been carried out. Once it has been assumed that an irreversible gas-liquid reaction is developed between ozone and the matter present in the water, the film theory concept was applied to this system for kinetic determinations. The evolution of the organic and inorganic matter with ozonation time has been followed by the chemical oxygen demand. The procedure allows the determination of the rate coefficients of ozone with the wastewaters treated. According to the results obtained, ozone is consumed through fast reactions which take place near the water-gas interface during an initial period. This period is used to determine the rate coefficients. Then, at more advanced ozonation times, the reactions become slower and hence they take place in the bulk of the water, articularly for the case of tomato wastewaters. Values of the rate coefficient allow us to establish both the kinetic regime of absorption and to compare the reactivity of ozone with the wastewaters and single compounds.     

Oxidation of Organic Pollutants of Water to Mineralization by Catalytic Ozonation

The oxidation of various organic compounds in aqueous solution was studied using catalytic ozonation (TOCCATA process) and conventional ozonation. The aim of the work is to assess catalytic ozonation efficiency for the mineralization of various organic compounds in order to envisage its application on real effluents. The selected organic compounds (about 30) are commonly found in industrial wastewaters. Comparative experiments were performed in batch mode at laboratory scale. Investigations were focused on ozone consumption rate, variations of total organic carbon, oxidation by-products and oxidation rate. Catalytic and conventional ozonation treatments were compared considering kinetic data, mineralization extent, and effect of organic functionalities. Catalytic ozonation system according to the TOCCATA process was able to convert organic compounds which were totally inert to ozone treatment and permitted considerably enhanced reaction rates when compounds were reactive to ozonation.     

Kinetic Description of Industrial Wastewater Ozonation Processes

Literary and experimental data on the ozonation kinetics of aqueous solutions and wastewater were analyzed. COD was suggested to be used as a kinetic parameter from the solution side. On the basis of the results obtained from the ozonation of model solutions and wastewater, the rate coefficient by COD of the reaction was shown to be constant during separate stages of the process. Due to the consumption of fast-reacting components and entering into the reaction of more slowly reacting intermediate products, the rate coefficient changed spasmodically with transition from one stage to another. The reaction order with respect to the COD of the solution was shown to be equal to the reaction order with respect to the pure component.     

Removal of Pesticides by a Combined Ozonation/Attached Biomass Process Sequence

Different combinations of ozonation and biological treatments were tested on an industrial effluent containing high pesticide concentrations. Ozonation was performed in 450 L columns at 1.5 h HRT each. Biological treatment was carried out in a submerged filter (BIOFOR). Ozone was effective in removing herbicides but dosages up to 1000 mg L^?1 were needed. The improved biodegradability of the organic compounds after pre-ozonation was demonstrated by Oxygen Uptake Rates (OUR) tests and by the efficiency of biological treatment towards COD, and pesticides. The Italian discharge limit of 50 ppb total pesticides was achieved by combining pre-ozonation, biological treatment, and post- ozonation.     

Modelling Industrial Wastewater Ozonation In Bubble Contactors. 1. Rate Coefficient Determination

A study of the ozonation of distillery and tomato wastewaters was carried out in a small bubble contactor in order to obtain kinetic data for scaling-up. Thus, several parameters, such as chemical oxygen demand (COD), 254 nm absorbance (A₂₅₄) and organic carbon content (OC), were followed during ozonation at different experimental conditions.

For distillery wastewaters all parameters investigated have the highest decreases during the first minutes of ozonation, A₂₅₄ showing the highest disappearance rates. Thus, during the first fifteen minutes of ozonation an important decrease of the 254 nm absorbance (? 75%) was observed. At further reaction times values of all parameters studied decrease slowly, eventually reaching a plateau value. During approximately the first two hours of reaction, dissolved ozone was never found, which suggested that fast or moderate gas-liquid reactions took place in the wastewaters.     

Modelling Industrial Wastewater Ozonation In Bubble Contactors. 2. Scale-up From Bench To Pilot Plant

A kinetic model constituted by ozone mol balance equations both in the gas and in the water phases and a total mole balance equation has been applied to predict concentrations of dissolved ozone, C_o3, ozone partial pressure at the reactor outlet, P_(o3)0, and remaining chemical oxygen demand, COD, for the ozonation of two industrial wastewaters released from distillery and tomato processing plants.

Kinetic equations for ozone absorption rate present in the model were derived from the application of film theory to an irreversible gas-liquid reaction. Parameters involved in the model, reaction rate and mass transfer coefficients, Henry's law constant, etc., were estimated from bench-scale experiments. The model was applied to ozonation in bubble contactors of height/diameter ratio equal to that of the bench scale contactor and to a pilot plant bubble column of a height/diameter ratio about 3.6 times higher.     

Ozonation of Anionic and Non-ionic Surfactants in Aqueous Solutions: Impact on Aquatic Toxicity

The objective of this study was to investigate the influence of ozonation of anionic and non-ionic surfactants on their aquatic toxicity. Toxicity values of various commercially important anionic and non-ionic surfactants have been determined using the luminescent bacterium Vibrio fischeri. Surface tension measurements were made to study the interfacial activity. The behavior depends on the chemical structure. Some intermediate ozonation products were found to be more toxic than the base surfactant and others were found to be less. Surfactants with aromatic rings such as linear alkyl benzene sulfonates, or surfactants with glycosidic groups such as alkylpolyglucosides, exhibit a lower toxicity after ozonation. On the other hand, ether groups present in the fatty-alcohol ethoxylates and ether carboxylic derivative surfactants, and carboxylic acid derivates present in the ether carboxylic derivative surfactants lead to increasing toxicity after ozonation. Surfactants with ether groups probably formed short-chain polyethoxylated compounds and carboxylic acids, which are possibly responsible for the surface-tension decrease that promotes the toxicity increase.     

Removal Characteristics of Organic Pollutants in Sewage Treatment by a Pre-Coagulation,Ozonation and Ozone/Hydrogen Peroxide Process

The applicability of a sequential process of ozonation and ozone/hydrogen peroxide process for the removal of soluble organic compounds from a pre-coagulated municipal sewage was examined. 6–25% of initial T-COD_Cr was removed at the early stage of ozonation before the ratio of consumed ozone to removed T-COD_Cr dramatically increased. Until dissolved ozone was detected, 0.3 mgO₃/mgTOC₀ (Initial TOC) of ozone was consumed. When an ozone/hydrogen peroxide process was applied, additional COD_Cr was removed. And we elucidated that two following findings are important for the better performance of ozone/hydrogen peroxide process; those are to remove readily reactive organic compounds with ozone before the application of ozone/hydrogen peroxide process and to avoid the excess addition of hydrogen peroxide. Based on these two findings, we proposed a sequential process of ozonation and multi-stage ozone/hydrogen peroxide process and the appropriate addition of hydrogen peroxide. T-COD_Cr, TOC and ATU-BOD₅ were reduced to less than 7 mg/L, 6 mgC/L and 5 mg/L, respectively after total treatment time of 79 min. Furthermore, we discussed the transformation of organic compounds and the removal of organic compounds. The removal amount of COD_Cr and UV₂₅₄ had good linear relationship until the removal amounts of COD_Cr and UV₂₅₄ were 30 mg/L and 0.11 cm^?1, respectively. Therefore UV₂₅₄ would be useful for an indicator for COD_Cr removal at the beginning of the treatment. The accumulation of carboxylic acids (formic acid, acetic acid and oxalic acid) was observed. The ratio of carbon concentration of carboxylic acids to TOC remaining was getting higher and reached around 0.5 finally. Removal of TOC was observed with the accumulation of carboxylic acids. When unknown organic compounds (organic compounds except for carboxylic acids) were oxidized, 70% was apparently removed as carbon dioxide and 30% was accumulated as carboxylic acids. A portion of biodegradable organic compounds to whole organic compounds was enhanced as shown by the increase ratio of BOD/COD_Cr.     

Understanding the Effects of Ozonation on a Combined Municipal/Industrial Secondary Effluent

An increase in the biodegradability of secondary effluent after ozonation as measured by CBOD₅ (carbonaceous BOD₅), generally has been considered to be due to the conversion of non-biodegradable organic material. Experiments on a specific combined unicipal/industrial waste containing a high percentage of malting plant wastewater showed that an increase in CBOD5 realized at the waste treatment plant was due to a shift in the oxygen uptake curve. Ozonation was found to affect both non-biode-gradable and biodegradable organic matter and resulted in improved overall effluent quality despite the observed increase in CBOD₅. As an indication of effluent quality, the CBOD₅ test is felt to be inadequate.     

Intrinsic Activity of SBA-like Silica in the Catalytic Ozonation of Organic Pollutants

Hydrothermal synthesis using two gel compositions: i. 1 SiO₂: 0.059 P123: 56.130 HCl: 607.638 H₂O; ii. 1 SiO₂: 0.006 P123: 0.013 F127: 42.439 HCl: 442.876 H₂O, resulted in highly crystalline SBA-15 and SBA-16 like silica with intrinsic activity in the catalytic ozonation of oxalic acid (OA), phenol (φ-OH) and Orange G (OG) in water at room temperature. X-ray diffraction, nitrogen adsorption–desorption, transmission and scanning electron microscopies revealed highly ordered mesoporous structure, with large surface area, regular channels and uniform particle size. UV-Vis analysis provided faster, more precise and reliable assessments of the decomposition yield and process selectivity than the conventional and laborious method of Chemical Oxygen Demand (COD). The ozone reactivity was found to be favored by increasing size of the organic substrate. OG and phenol decomposition required shorter ozonation time (20, 15 min, respectively) than OA, involving mainly phenyl ring hydroxylation and cleavage. Measurements through thermal programmed desorption of carbon dioxide and water revealed that the catalytic activity of the SBA samples involves adsorption via both acid-base and hydrophobic interactions. Suitable SBA modifications allow tailoring these interactions for even faster ozonation without persistent traces of short chain derivatives.     

Oxidation of Emerging Contaminants during Pilot-Scale Ozonation of Secondary Treated Municipal Effluent

The transformation of 41 target emerging contaminants in secondary treated municipal wastewater effluent in Canada was examined at pilot-scale, at transferred ozone doses of 2.8 mg/L (0.46 O₃/mg DOC) and 4.4 mg/L (0.72 mg O₃/mg DOC). In general, transformation efficiencies of CECs either increased or were retained at the higher ozone dose. The higher ozone dose of 0.72 mg O₃/mg DOC (Z_spec = 0.6 mg O₃/mg DOC) was sufficient to transform 21 of the 31 detected CECs by over 80% as well as achieving the disinfection target of < 200 MPN E. coli per 100 mL.     

Study on By-Products of Ozonation during Ammonia Removal under the Existence of Bromide: Factors Affecting Formation and Removal of the By-Products

Factors affecting the formation of by-products of ozonation during ammonia removal under the existence of bromide were investigated. The presence of reducible N compounds could significantly reduce the formation of bromate and brominated organics; however, it was difficult to completely prevent formation of the by-products. It was therefore concluded that while the method used in this study was an effective process to decompose ammonia, it should be applied to the treatment of wastewaters containing low concentration of TOC. For power plant condensate demineralization wastewater containing TOC of 3 to 4mg/L, TOX formed during ammonia removal ranged from 0.20 to 0.30 mgBr L^?1. The only halogenated organic substance of the power plant wastewater detected on GC spectrum was bromoform, whose concentration varied from 0.11 to 0.14 mg L^?1. Column test results indicated that bromate could almost completely be decomposed to bromide by activated carbon under proper space velocity and pH. Activated carbon was also very effective in adsorption of CHBr₃: 1 g activated carbon adsorbed ca. 20.3 mg of CHBr₃.     

Oxidation of Cyanuric Acid in Aqueous Solution by Catalytic Ozonation

The aim of this work was studying the activity of a Ru/CeO₂ powder catalyst in the ozonation of aqueous solution of cyanuric acid (CYA). Ozonation in the presence of the catalyst significantly enhances CYA degradation. Within this work, investigation of the influence of pH and initial concentration on the catalytic ozonation of CYA has been done in a semicontinuous reactor. The removing degree of CYA at pH 5.9 show better response in comparison to pH 2.5 and pH 8.2. The mineralization of CYA by catalytic ozonation formed nitrate ions (0.7 mol of NO₃^?/mol of CYA removed for 50% initial CYA abatement) and nitrite and ammonium ions in small amounts. Three transformation products formed during catalytic ozonation were identified from LC/MS and MS/MS analyses. The impact of oxidation on the toxicity was measured from the inhibition of Vibrio fisheri, which was found to increase continuously.     

Ozonation of Trace Organic Compounds: Model Predictions versus Experimental Data

This paper is focused on the use of ozone for the elimination of manmade organic micropollutants from drinking waters and waste effluents requiring advanced treatment. A mathematical model was developed to simulate the physical transport and chemical oxidation phenomena prevailing during the process of ozonation. A packed column reactor was constructed in order to test the aptness of the process model. After determining the fluid-dynamic and mass transfer properties of the reactor, stock water solutions spiked with toluene were brought into contact with gaseous O₂-O₃ mixtures. Toluene removal efficiencies observed under different experimental conditions then were compared with the model predictions.     

Effect of Catalytic Ozonation Coupling with Activated Carbon Adsorption on Organic Compounds Removal Treating RO Concentrate from Coal Gasification Wastewater

This paper reports a novel system of catalytic ozonation coupling with activated carbon adsorption for removing the organic compounds treating in the RO concentrate from coal gasification wastewater. The effect of ozone dosage, catalyst dosage, reaction time, influence pH, and temperature on organic compounds removal were examined for the processes. In the catalytic ozonation process, increasing solution pH, dosages ozone, and catalyst were statistically significant for improving the performance. In addition, the high salinity with chloride concentration of 15 g/L could reduce the catalyst specific surface area by 18%. Thus, high salinity showed negative influence on the catalytic effect in TOC removal. Regarding activated carbon adsorption process, modified activated carbon by NaOH revealed advantages in adsorbing organic compounds treating catalytic ozonation effluent. With the ozone dosage of 120 mg/L, catalyst dosage of 2.0 g/L, catalytic ozonation reaction time of 1 h, and modified activated carbon adsorption time of 1 h, the average TOC removal efficiencies were maintained at the stable level of 58% with the TOC concentration of 26 mg/L.     

Sequential Partial Ozonation for the Treatment of Wastewater Concentrate: Practical Implications From a Conventional and (Eco) Toxicological Perspective

This article compares multi-stage ozonation-biological treatment processes [O₃ - Biodegradation - O₃ - Biodegradation] and conventional partial ozonation processes [O₃ - Biodegradation] for the removal of S_COD and toxicity from a recalcitrant and toxic wastewater concentrate. Both direct (pH 7.5) and advanced (pH 11.5) ozonation are evaluated. Short-term estimation methods for biodegradability (respirometry) and toxicity (30 min Vibrio fisheri luminescence inhibition) are evaluated for their use in process control.     

Biodegradability Improvement of Aqueous 2,4-Dichlorophenol And Nitrobenzene Solutions By Means of Single Ozonation

The possibility of the integration of ozonation and biological processes as an economical way to treat biorecalcitrant organic compounds such as nitrobenzene and 2,4-dichlorophenol was investigated. In the pre-treatment step, stoichiometric coefficients and pseudo first-order kinetic constants were obtained. Biodegradability was monitored throughout the ozonation step, in order to evaluate the optimum ozone doses. The low TOC reduction after these ozone doses allowed much of the organic carbon to be removed in the biological stage. In the case of 2,4-dichlorophenol, the biodegradability improvement was checked in an aerobic bioreactor. By means of the combined ozonation-biological oxidation, up to 80% of the initial organic content was removed. Results presented in this study show the feasibility of using the combination of ozone and conventional biological treatments to treat wastewaters containing these pollutants.     

Ozonation Reactions of Monomer and Dimer Lignin Models: Influence of a Catalytic Amount of a Manganese Cyclam Derivative on the Ozonation Reaction

This work focuses on the study of the reactivity of ozone with lignin models such as vanillin and dehydro-di-isoeugenol (DHDIE) in methanol solution. The primary by-products formed are characterized by Gas Chromatography - Mass Spectrometry (GC-MS) and possible mechanisms for the formation of these by-products are suggested. In the presence of a catalytic amount of a manganese tetraazamacrocyclic complex, other degradation derivatives are identified during DHDIE ozonation, proving that the complex induces a different reactivity of ozone towards the model.     

Comparison between Ozonation and Photo-Fenton Processes for Pesticide Methomyl Removal in Advanced Greenhouses

So-called “Advanced Greenhouses” are a new approach to the concept of protected agriculture. Among other technological and structural improvements, these facilities give the possibility of recycling the irrigation surplus water, rich in lixiviates, salts, pesticides and its metabolites. After many cycles, the current is so concentrated on those substances that it becomes necessary for the presence of a membrane separation stage which brine, highly concentrated on those named pollutants, has to be treated before being sent to the public sewage system. Advanced Oxidation Processes, among other chemical treatments, can be considered an alternative to process this current effluent. In this work, concentrated aqueous solutions of methomyl as model pesticide (200 mg·L^?1) have been subjected to two of those processes: ozonation and photo-Fenton reaction. Analysis of the elimination of the pesticide itself and the grade of mineralization achieved have shown how, while the ozonation is the most effective process decomposing the pesticide (eliminating the total concentration in 60 minutes), the photo-Fenton reaction mineralizes successfully the 40% of the total organic load (the ozonation only can cope with 20%) but only decompose a 40% of the pesticide. Evolution of biodegradability and toxicity of the effluent along both processes was also analyzed. Intermediates generated both by ozonation and photo-Fenton did not increase the biodegradability of the treated effluents. Nevertheless, while acute toxicity just after 15 minutes of treatment with ozone is notably higher than for raw solution, and it is maintained till the end of the experiment (120 min), though, toxicity along photo-Fenton reaction has two growing and decreasing regions, always shows lower values than the provoked during ozonation. None of the two assayed processes has been proved to increase biocompatibility of highly concentrated methomyl solutions.     

Cellular Toxicity and Mutagenicity Assays from On-Site Sampling of Drinking Water Treatment Plants Using Multistage Ozonation

Studies were carried out on-site in a potable water production plant utilizing ozonation treatment at three stages of the process. The quality of water in the treatment line was studied by chemical analysis, but also for toxicity to Hela cells after XAD resin concentration, and for mutagenesis to Salmonella Ames strains and mammalian cells V79 HGPRT system. With a sufficient dose of ozone and activated carbon adsorption, the initial cytotoxicity of the raw water and the mutagenic or promoter activity are destroyed.