臭氧在对硝基苯酚溶液中的吸收与模拟过程

研究了鼓泡塔中臭氧在对硝基苯酚溶液中的吸收传质过程。首先探讨了pH值和气速对对硝基苯酚降解速率的影响。在 298K下,臭氧被连续通入对硝基苯酚溶液中,臭氧的传质速率因为溶解臭氧与对硝基苯酚的快速反应而大大加强。然后运用与实验条件相同的操作参数,进行了臭氧在鼓泡塔中吸收过程的模拟研究,采用MATLAB软件求解吸收过程的质量平衡方程,模拟了吸收过程中臭氧和对硝基苯酚浓度的变化,并与实验值进行了比较。结果表明,在短的鼓泡塔中,应用全混流模型来描述气相和液相的流体状态是可行的,在 80%的对硝基苯酚降解之前,模拟值和实验值能很好地一致。     

OZONE TREATMENT OF METHYLENE BLUE IN AQUEOUS SOLUTIONS

The kinetics of ozonation of the sulfur dye Methylene Blue in aqueous solution is studied. The experiments have been carried out in a bubble column, using a single nozzle as gas sparger. The influence of the operating variables (initial concentration of Methylene Blue, ozone partial pressure, temperature and pH) on the oxidation process is established. A stoichiometric ratio of 3 moles of ozone consumed per mol of dye reacted is deduced. A reaction scheme based on the direct ozone attack to the dye is suggested, and it agrees with the found stoichiometry. The overall reaction orders and rate constants as a function of pH and temperature are determined following the film theory which is applied to the experimental data. The process develops in the fast pseudo mth order kinetic regime of absorption.     

Influence parameters in the ozonation of phenol wastewater treatment using bubble column reactor under continuous circulation

The ozonation of phenol wastewater treatment system has been investigated with effective mass transfer between gas and liquid phase in a bubble column reactor. The designed bubble column reactor was investigated for increasing the rate of mass transfer of ozone, the rate of oxidation of phenol in the solution, the solubility and decomposition rate of ozone in the distilled water were also studied at different flow rates. The decomposition rate constants were calculated based on pseudo first order kinetics. The oxidation of phenol was investigated in order to provide the overall reaction rate constant for the reaction between ozone and phenol at 25 °C. The influence of the operating parameters like initial phenol concentration, ozone flow rate and pH for the destruction of phenol by ozonation were studied. The pseudo first order rate constant was depending on the initial concentration of phenol solution. A comparison of TOC removal percentage between bubble column reactor and bubble diffuser using ozonation were reported.     

Evaluating Dissolved Ozone in a Bubble Column Using a Discrete-Bubble Model

Ozonation has been widely applied in water treatment plants, so it is essential to figure out mass transfer and reaction kinetics in ozone contact tanks. In this study, a discrete-bubble model was established to calculate the dissolved ozone concentration in a countercurrent flow system. Results from batch experiments showed that an exponential relationship was well fitted between ozone reaction rate coefficient and ozone consumption amount, and the relationship was not affected by the ozone dosage. Therefore, it was applied in a discrete-bubble model, which was validated by experiments in a countercurrent bubble column with error less than 15%.     

Comparing Different Designs and Scales of Bubble Columns for Their Effectiveness in Treating Kraft Pulp Mill Effluents

The experimental results obtained in three different types of ozone contactors were analyzed to study the effects of the ozone contactor design, configuration, operating conditions, and scale-up on the: (1) ozonation process induced reduction efficiencies of color, AOX, COD, and TOC from biologically treated Kraft pulp mill effluents; (2) the increase in biodegradability of this type of wastewater; and (3) the dynamics of the ozone gas absorption process. The three types of ozone contactors included: (1) an extra-coarse-bubble diffuser ozone contactor; (2) an impinging-jet ozone contactor; and (3) a fine-bubble diffuser ozone contactor. Similar treatment levels were achieved in those ozone contactors although the impinging-jet bubble column was more effective in treating Kraft pulp mill effluents due to its smaller reactor volume and lower off-gas ozone concentrations. Consequently, the operating costs of an ozonation process and ozone off-gas destruction facilities will be greatly reduced when using the impinging-jet bubble column design for treating Kraft pulp mill effluents.     

Ozonation of C.I. Reactive Black 5 and Indigo

The ozone transfer for the ozonation of the azo dye Reactive Black 5 (RB5) and indigo was investigated using a bubble column at semi-batch conditions. The results were analyzed by applying film theory and surface renewal theory. The ozonation of both dyes was so fast that an instantaneous reaction directly at the bubble surface can be assumed. The ozone balance in the gas phase was used to determine the volumetric mass transfer coefficient k_La and the enhancement factor E. Besides the measured concentrations, temperature and pressure only the Henry coefficient was required for the determination of k_La and E. By varying the ozone inlet and the dye concentration the reaction regime was identified. The Hatta number Ha which requires uncertain parameters did not have to be determined.     

Axial Dispersion Model for Estimation of Ozone Self-Decomposition

A new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semibatch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with literature data. The reaction order in the pH range 7–10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. A sensitivity analysis was conducted to obtain information on reliability and identifiability of the estimated parameters.     

Design and Modeling of a Staged Downflow Bubble Reactor

A staged downflow bubble column for ozonation of drinking and wastewater was developed. Equations for the calculation of head loss, the mass transfer coefficient, and power dissipation were proposed For mathematical modeling, the stagewise backmixing model was used. The validity of the model was verified by experiments with raw lake water Ozone absorption in a staged downflow bubble column was shown to represent a high capacity process for ozone uptake in water and wastewater treatment.     

An Experimental Study Of Ozonation Followed By Slow Sand Tiltration for the Removal of Colour from Water

Ozone was introduced into the water initially using a packed colum, however, in order to improve the ozone utilisation it was decided to change to a spilt ozone dosage arrangement using a counter flow bubble column followed by a packed colum. Subsequent tests showed that the bubble colum alone produced similar ozone utilisation to the split dosing arrangements and the last 6 test runs were all undertaken using the bubble ozone alone.     

Multiphase reacting flow studies of bubble column ozonation reactor for water remediation

A multiphase Volume‐of‐fluid (VOF) model was developed to gain further insights into the reactive flow parameters and electrical capacitance tomography (ECT) measurements on the remediation of hazardous organic pollutants. Low ozone bubble frequencies were obtained for high surface tension fluids, and the liquid viscosity affected the ozone bubbling frequency. The VOF model indicated that the increase of inlet gas velocity enriched the ozone bubble detachment and concomitantly generated larger ozone bubbles, decreasing the detoxification rates. VOF mappings and ECT visualizations of gas‐liquid unveiled preferential routes and highlighted the attenuation of the axisymmetric behavior of the ozonation bubble column under high‐interaction regimes.     

Mass Balance Analysis of Ozone in a Conventional Bubble Column

Ozone transfer into potable water was studied in a conventional bubble column, and ozone mass balances have been calculated to determine ozone utilization efficiencies. Liquid and gas flow rates, as well as inlet ozone concentrations in the gas phase were varied. Using these data, it was possible to determine the ozone mass transfer coefficient, ozone transfer efficiency, and ozone consumption. A model of ozone transfer was established, and procedures for calculating the optimum design parameters and operating conditions are proposed.     

Modeling Ozone Reaction Rate Constants of Micropollutants Using Quantitative Structure-Property Relationships

A quantitative structure-property relationship model was developed using piecewise linear regression (with two submodels) to predict second-order rate constants with ozone for a wide range of structurally diverse micropollutants. The model was developed using a set of pre-selected structurally diverse micropollutants for which rate constants had been determined experimentally, and then validated with an external data set. A classification function was developed using linear discriminant analysis to classify micropollutants into high-reactive or low-reactive compounds before using the appropriate submodel. The applicability domain of the model was determined using the Williams plot.     

Dynamic Performance of Ozonation Treatment for Nonionic Surfactants (Polyoxyethylene Alkyl Ether) in a Bubble Column Reactor

The ozonation of a nonionic surfactant, Sannonic SS-90 (polyoxyethylene alkyl ether), which is one of polyoxyethylene nonionic surfactants, in water has been investigated using a bubble column. The effects of initial nonionic surfactant concentration, ozone gas flow rate, inlet ozone concentration in the gas-phase, liquid-phase temperature and hydrogen peroxide dose on decomposition of Sannonic SS-90 were systematically examined. The decomposition rate of Sannonic SS-90 decreased with the increase in the initial surfactant concentration and increased with increasing ozone flow rate and temperature. It was found that the rate of Sannonic SS-90 mineralization was weakly dependent on the gas-phase inlet ozone concentration in the range of the gas-phase inlet ozone concentration in this study. The oxidation rate increased with increasing concentration of H₂O₂, reached a maximum value and then decreased with further increasing of H₂O₂ concentration. The dynamic performance of the ozonation in a semi-batch bubble column was simulated using a mathematical model based on a tanks-in-series model. Reasonable agreement between the present experimental data and the simulated results was found.     

Hydrodynamics and ozone mass transfer in a tall bubble column

In the paper, major hydrodynamic parameters such as gas hold-up, phase velocities and axial dispersion as well as the ozone mass transfer coefficients in the liquid phase have been investigated in a tall bubble column for co-current, counter-current and semi-batch modes of operation. The major emphasis has been placed on evaluation of the dynamic characteristics of the combined system of experimental column and measuring sensors, which was applied in the subsequent determination of the axial dispersion and ozone mass transfer coefficients in the liquid phase. The ozone mass transfer coefficients have been estimated using two treatment methods of the recorded changes of ozone concentration in the liquid and gas phases with time during ozone absorption or stripping to an inert gas.     

Hydrodynamik in Blasensäulen – Messung von relativem Gasgehalt und Blasengröße

In bubble column reactors mass transfer kinetics are determined by local hydrodynamic processes (bubble formation, velocity, coalescence, break‐up, etc.). For a better understanding of the influence of pressure and particle load on these processes, a measurement system for detection of local bubble size distributions in opaque bubbly flows is needed. Therefore, in this work an optical needle probe was applied in a bubbly flow. In a first step, the needle probe was validated by means of single‐bubble measurements. The measurement technique shows high potential for application in more complex and opaque systems.     

Catalysts to improve the abatement of sulfamethoxazole and the resulting organic carbon in water during ozonation

Sulfamethoxazole (SMX), one pharmaceutical compound, has been treated in aqueous solutions with catalysts (copper and cobalt type perovskites and cobalt–alumina) and promoters (activated carbons). Hydrogen peroxide and saturated carboxylic acids were identified as intermediates. The effects of adsorption and pH have been investigated. Removal of the starting SMX accomplished with ozone alone is a fast process but catalytic or promoted ozonation is needed to significantly reduce the resulting organic carbon. SMX is, thus, mainly removed through direct ozone reaction while hydroxyl radical oxidation is the mechanism of removal the remaining TOC. The kinetics of the process has also been investigated. Perovskite catalytic ozonation resulted to be a chemical control process and apparent rate constants for homogeneous and heterogeneous ozonation were determined. For activated carbon ozonation, external diffusion of ozone to solid particles controlled the process rate.     

Removal of Residual Dissolved Ozone with Manganese Dioxide for Process Control with UV254

Ozonation is one of the most promising options to remove organic micropollutants (OMP) from wastewater treatment plant effluents. For an economic operation and in order to avoid formation of bromate, the ozone dose has to be adjusted in real-time due to the strongly varying effluent quality. The reduction of UV absorption at 254 nm (?UV₂₅₄) is a useful surrogate parameter for OMP removals. Unfortunately dissolved ozone also absorbs UV at 254 nm and therefore might disturb a ?UV₂₅₄-based process control. A fixed bed of manganese dioxide granules was found to efficiently remove residual ozone.     

Use of the axial dispersion model to describe the O3 and O3 /H2O2 advanced oxidation of alachlor in water

Experiments on alachlor degradation by ozonation alone and combined with hydrogen peroxide using different surface waters have been conducted in a reactor bubble column and a kinetic model of the advanced oxidation process has been proposed. Variables studied were the nature of the surface water (four surface waters were treated), pH (3.5–9.7) and hydrogen peroxide to ozone mass ratio at the column inlet (0.1–1.85 g g^?1). Data on residence time distribution, rate constants and the absorption kinetic regime were considered to prepare the kinetic model, which was also based on the axial dispersion model of non‐ideal flow. The model gives good predictions of alachlor and hydrogen peroxide conversions and the fraction of dissolved ozone (deviations were lower than ±15%) although it fails, in some cases, to yield accurate estimates of the observed experimental trends of concentrations in water at the reactor column outlet. The calculated results were close to those obtained from the more classical N well‐mixed tanks‐in‐series model (deviations with this model were lower than ±20%). It is concluded that quantitative deviations from experimental observations were likely due to the lack of rate data on ozone reactions with organic matter present in the surface waters investigated. © 2002 Society of Chemical Industry     

INVISCID LIQUID CIRCULATION IN BUBBLE COLUMNS

For circulation in axi-symmetric (cylindrical) bubble columns, the recently developed mathematical model^25,26 has been used along with the criterion of minimum circulation strength to determine the height of each circulation cell in a tall column. This is then used to derive a theoretical expression, first of its kind, for gas hold-up inside a bubble column. The predictions of this equation as well as the equation derived here for axial liquid velocity at column axis have been compared with available data and the comparison is found to be excellent for both the variables. An explicit relation is derived for the average liquid circulation velocity. The model is also used to derive an expression for liquid axial dispersion coefficient which compares almost exactly with Deckwer et al.'s⁴ correlation.

For circulation in two-dimensional bubble columns a new mathematical model is developed. The predictions of bubble envelope shape and bubble envelope area compare well with published data. The predictions of number of circulation cells in the horizontal direction also compare well with published data.     

Intensification of nitrous acid oxidation

An alternative solution to the reduction of a discharge of residual nitric oxide and nitrogen dioxide into atmosphere has been proposed. Instead of using methane or ammonia for SCR or gas absorption into alkali solutions, which are the most popular treatment methods of tail gases, now the use of powerful oxidant—ozone capable of transforming nitrous acid and nitric oxides into nitrogen of the highest oxidation level—could be employed for this purpose. As the intensive oxidation and ozonation of nitrous acid is the heterogeneous gas-liquid process, the solubility of oxygen and ozone in HNO₂/HNO₃ aqueous solution was necessary to be determined. Variations of reaction rates depending on temperature, ozone dose and nitrous and nitric acid concentrations were studied experimentally. The kinetic model of the reactions, 2HNO₂+O₂→2HNO₃ and HNO₂+O₃→O₂+HNO₃, were proposed and the kinetic parameters (rate constants and activation energies) were estimated on the basis of experimental data in semi-batch laboratory gas-liquid contactor with the liquid phase drawn from an absorption column in the nitric acid plant. The determined kinetic parameters were then used in designing and modeling of the oxidation of nitrous acid using ozone-oxygen mixture in a continuous bubble column. The model consists of mass transfer kinetic equations and material balance equations for the gas and liquid phases. The co-current flow of gas and liquid phases and the complex kinetics of chemical reaction in the liquid phase were taken into account. The variation of the following process conditions, flow rate, compositions of the gas and liquid phases, temperature, and pressure in the bubble column of different diameters and heights, were studied in numerical solutions of the proposed model.