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.     

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.     

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.     

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.     

Improved Sludge Dewaterability for Sequential Ozonation – Aerobic Treatment

Chemical treatment processes such as ozonation have mostly been considered as an efficient way for bio-solids minimization. The improvement of sludge dewatering was more a welcoming side-effect in these sequential processes. However, sometimes the loaded ozone dose to the sludge has a negative effect on dewaterability. This work address the most important issue found — the effect of ozone on sludge dewaterability in a single ozonation processes as well as in a sequential ozonation biological processes. It was found that the maximum sludge dewaterability was achieved with an ozone dose of 0.05 gO₃/gTSS. This value was found to be less than the required ozone dosage that leads to sludge disintegration. However, it was observed that the sequential ozone and aerobic treatment allows further strong improvement of dewatering efficiencies.     

Comparison of Aqueous Ozone and Chlorine as Sanitizers in the Food Processing Industry: Impact on Fresh Agricultural Produce Quality

The effects of ozone treatment on fresh strawberry and shredded lettuce food quality were tested by varying applied ozone concentration, contact time, pH and temperature to assess ozone a potential food sanitizer. The produce quality was assessed by comparing the changes in texture firmness, browning and decolorization, oxygen consumption and carbon dioxide respiration after the post-treatment storage from 0 to 21 days. The effectiveness of ozonation on natural microfloras including mesophiles, psychotrophes, yeasts and molds, was also evaluated for the improvement in produce shelf-life. As compared to chlorine treatments, ozone treatments slightly increased the lettuce browning but substantially retarded its respiration rates and firmness deterioration even after 21 days of storage. For strawberry, no significant difference in food quality was observed between ozone and chlorine treatments. Finally, ozone treatments at the doses below 10 mg/L were found not effective in killing natural microfloras grown on the produce surfaces.     

臭氧/活性炭处理炼油废水的初步研究

考察了可能在实际水处理过程中影响O3 活性炭催化氧化工艺处理效果的因素 ,结果表明该工艺将臭氧的强氧化能力与活性炭的吸附、催化能力有机的结合到了一起 ,利用活性炭的催化作用来提高臭氧化的能力 ,使废水的处理效果大为改观 ,该工艺具有一定的可行性     

Performance evaluation of pretreatment processes in integrated membrane system for wastewater reuse

A series of lab-scale filtration experiments were performed under various operating conditions to investigate the fouling behavior of microfiltration (MF) membranes when employing two different pretreatment methods. The secondary effluents from a biologically advanced treatment process were fed to each hybrid system, consisting of coagulation-flocculation-MF (CF-MF) and ozonation-MF processes. All experiments were carried out using a stirred-cell system, which consisted of polyvinylidene difluoride (PVDF) MF membranes with a 0.22 μm pore size. When MF membrane was used alone without any pretreatment, the permeate flux dropped significantly. However, in the case of employing polyaluminium chloride (PACl) coagulation and ozonation as a pretreatment, the extent of flux decline rates was enhanced up to 88 and 38%, respectively. In the CF-MF hybrid system, the removal efficiencies of COD and total phosphorus were significantly enhanced at a coagulant dose above 30 mg/L. With ozonation, more than 90% of the color was removed even at a low dosage of ozone (5 mg/L). Therefore, ozonation would be strongly recommended as a pretreatment in terms of removing organic matter. The permeate water quality by ozonation-MF process was in good compliance with the guidelines for wastewater reuse proposed by South Korean Ministry of Environment.     

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.     

Intermittent Ozone Application in Aerobic Sludge Digestion

Excess biological sludge, WAS, produced during activated sludge process is a growing problem for the utilities owing to the stringent regulations now imposed worldwide. One method of handling the excess sludge is to digest it, to reduce its amount and to stabilize it. Aerobic digestion is particularly suitable for nutrient treating plants as sludge should not be exposed to anaerobiosis since this will lead to release of accumulated phosphorus. A novel and patented ozone-assisted aerobic sludge digestion process (PCT/TR2010/000213) is shown to appreciably shorten the 15–30-day aerobic digestion period and the extent of solids destroyed. WAS samples were ozonated for different periods in Erlenmeyer flasks, once a day, on each of four consecutive days. Flasks were continuously aerated between ozone applications. The MLVSS, MLSS, COD and OUR parameters were measured routinely during the course of four days of digestion in order to optimize the process. As a result 22.6%, 40%, 75% and 84% MLVSS reductions were obtained at total ozone applications of 0.42, 0.64, 0.85 and 1.27 mg O₃ g^?1 MLSS, at the end of the fourth day. Hence, it became possible to save on contact time as well as achieving a bio-solids digestion far exceeding the standard aerobic process, which is 40–50% in 15–30 days, at the expense of a minimum of ozone dose. The developed process is deemed superior over side-stream ozonation where ozone is applied to the return activated sludge, RAS, line; in that it does not cause any reduction in active biomass amount maintained in the aeration tank. Conversely, reduction in active biomass concentration results in reduced treatment efficiency.     

ON A SYSTEMATIC DESIGN PROCEDURE FOR SINGLE COMPONENT WATER UTILIZATION SYSTEMS IN PROCESS PLANTS

This paper presents a robust methodology to obtain an optimal design of the single component water/wastewater allocation problem in process plants. The method uses a concentration grid water allocation procedure to obtain preliminary optimal structures. A merging procedure provides the final structures. The use of different water allocation strategies shows that the problem has several alternative solutions.     

CAST工艺在大连凌水河污水处理厂的应用

介绍了大连凌水河污水处理厂CAST工艺设计参数和工艺特点,实际运行中进出水水质情况及运行效果。分析了CAST工艺的进水方式、曝气量、污泥浓度等运行参数对污水处理效果的影响。凌水河污水处理厂的运行结果表明,CAST工艺对城市污水有较好的处理效果,出水指标稳定达到了《城镇污水处理厂污染物排放标准》（GB18918-2002）一级B标准。     

Effect of hydrophilic/hydrophobic fractions of natural organic matter on irreversible fouling of membranes

Natural organic matter (NOM) has been identified as a major factor affecting membrane processes performances, but its impact is difficult to quantify from global parameters such as organic carbon content. The extent of fouling due to the different fractions of NOM from surface water has been examined in dead-end ultrafiltration using criteria such as flux decline and irreversibility in regard with organic matter rejection. The most important flux decline was observed during the filtration of the hydrophilic acids fraction whereas fulvic acids led to the most irreversible fouling. Furthermore, the hydrophilic fraction lost its fouling character when mixed with other fractions underlining that interactions between numerous components are possibly more important than the composition itself.     

Henry And Mass Transfer Coefficients In The Ozonation Of Wastewaters

A procedure for the determination of Henry and mass transfer coefficients in an ozone-industrial wastewater system is presented. The method is applied to the ozonation of a tomato plant industrial wastewater, developed in the slow kinetic regime. In so doing, molar balances of ozone (in gas and water phases) are used together with gas-liquid reaction kinetic theory. While Henry's coefficients obtained are similar to those corresponding to ozonation in organic-free water, significant deviations are observed regarding the mass transfer coefficient.     

Removal of residual organic matter from secondary effluent by iron oxides adsorption

Residual organic matter (ROM) removal is an important issue in wastewater reclamation and reuse processes. Use of iron oxide particles (IOPs) as adsorbents for further treatment of the secondary effluent was investigated to mainly remove non-biodegradable residual organic matter under various operating conditions. ROM removal by IOP adsorption was evaluated in terms of the changes of UV absorbance, COD, and DOC concentrations in feed (secondary effluent) and treated water. The respective relationship of UV removal with COD and DOC removal efficiencies exhibited somewhat different profiles, possibly due to the influence of ROM properties on adsorptive removal mechanisms by IOP, such as hydrophobicity and coordinative capability. The types of IOPs such as ferrihydrite, geothite, and hematite were compared, and it was found that amorphous ferrihydrite was most effective in ROM removal. Maximum ROM removal was occuring at a solution pH of approximately 6.0, which might be ascribed to the ability of ligand exchange related to the association and dissociation of ROM molecules and IOPs at differing pH levels. Substantial reduction in the oxidation state (OS) of the treated water at high ROM removal indicated the coordination of highly oxidized groups in ROM at the IOP surface, such as carboxylic groups.     

Effect of Ozonation on Activated Sludge Solubilization and Mineralization

New strategies for sludge stabilization and mineralization need to be developed since the use of sludge in agriculture is debatable and sludge incineration cannot be a systematic solution. Minimization of sludge production should be preferred. In this work, the effect of ozone on activated sludge solubilization and mineralization during batch experiments is assessed by establishing carbon and ozone mass balances. After extended ozonation of the sludge, more than 90% of the particulate carbon is modified. Depending on the experimental conditions, from 15 to 50% is found in a soluble form and from 35% to 95% was mineralized. The VSS/SS ratio decreases from 86% to less than 50% illustrating the sludge mineralization. The initial rate of ozone consumption by the sludge is very high (estimated value: 30 mgO₃/g VSS.min) and corresponds to high rates of carbon solubilization and mineralization. More than 50% of the carbon obtained after ozonation is found to be readily biodegradable using a short-term BOD procedure.     

Sludge Ozonation and its Application to a New Advanced Wastewater Treatment Process with Sludge Disintegration

The applicability of sludge ozonation on wastewater treatment processes was investigated to reduce the amount of excess sludge without losing phosphorus removal efficiency. Solubilization degree per ozone consumption for general sludge was in the range from 2.4 to 5.8 gSS/O₃ and from 4.1 to 7.7 gCOD/gO₃. Around 80 to 90% of solubilized organics was biodegradable at a solubilization degree of 0.3. Based on the experimental results, a lab-scale plant with sludge ozonation and phosphorus crystallization was constructed to investigate the treatment performance. Amount of excess sludge was reduced by 93% with almost complete removal of soluble BOD and phosphorus removal efficiency of more than 80%. The percentage of the effluent COD_Cr discharge increased from 10% to 14–17% after installing ozonation and crystallization because of the formation of non-biodegradable organic substances in ozonation process. Energy consumption of the innovative advanced process is comparable or can be even smaller than that of the conventional anaerobic/oxic (A/O) process in spite of the installation of ozonation and crystallization.     

Heterogeneous Catalytic Ozonation of Refinery Wastewater over Alumina-Supported Mn and Cu Oxides Catalyst

An economical method was proposed to develop an efficient alumina-supported manganese (Mn) and copper (Cu) oxides (Mn-Cu-O/Al₂O₃) catalyst with a high surface area, 184.06 cm² g^?1. The catalyst was utilized for degradation refinery wastewater by heterogeneous catalytic ozonation. The effects of various operating variables including pH, ozone and catalyst dosages, and temperature were systematically investigated in detail to obtain the optimized conditions for accelerated degradation of refinery wastewater. The optimum values were as follows: ozone dose 50.0 mg L^?1, catalyst dose 3.0 g L^?1, initial pH = 6.8, T = 17 °C. Refinery wastewater samples were analyzed by chemical oxygen demand (COD) and the results indicated that kinetics of COD followed a pseudo–first-order degradation. Moreover, hydroxyl radical mechanism rather than absorption was proposed, indicating that the surface hydroxyl groups were the active sites that played a significant role in catalytic ozonation.     

Natural organic matter and formation of trihalomethanes in two water treatment processes

The investigation involved the study of performance of two local plants' slightly different treatment processes for the removal of natural organic matter (NOM) which comprises trihalomethane (THM) precursors. Ultrafiltration separated the contained NOM into various apparent molecular weight (AMW) fractions to reveal the two processes NOM removal efficiencies, in terms of dissolved organic carbon (DOC), UV absorbance (UV254) and THM formation potential (THMFP). DOC and UV254 levels of source water at both plants tested low and they concentrated in the portion with AMW less than 3,000 Daltons. The combined expression of UV254 with DOC as specific ultraviolet light absorbance (SUVA) indicated that the source water of Macau had a value less than 3 L/mg-m. Therefore the main DOC content was fulvic in character, which is difficult to remove and favors the formation of brominated THMs. Low DOC removal percentages recorded in both processes confirm this observation. However, both processes showed similar removal efficiency of around 50% on humic substances and THM precursors quantified by measurements of UV254 and THMFP, respectively.