Oxidation of nitrobenzene by ozone in the presence of faujasite zeolite in a continuous flow gas-liquid-solid reactor.

This work investigates the oxidation of nitrobenzene (NB) by ozone in the presence of faujasite zeolite. Experiments were carried out in a gas-liquid-solid reactor were ozone transfer and NB oxidation took place at the same time. Three configurations of the reactor were compared: empty, filled with inert glass beads and filled with faujasite pellets. First, ozone transfer coefficient (k(L)a) and decomposition rate constant (k(C)) were determined for each configuration. In presence of solid, k(L)a was 2.0 to 2.6 times higher and k(C) was 5.0 to 6.4 times higher compared to the empty reactor. Then, the various configurations were evaluated in terms of NB removal and chemical oxygen demand (COD) decrease. The faujasite reactor showed higher removal of NB and decrease of COD compared to other configurations under the same conditions suggesting that the faujasite increases the oxidation rate of NB. Oxidation of NB in presence of faujasite also proved to be limited by the transfer of ozone from the gas to the liquid phase.

Enhanced bio-recalcitrant organics removal by combined adsorption and ozonation.

Removal of bio-recalcitrant and toxic compounds from wastewaters has been a major objective of industrial manufacturers for a few years. Due to the potential risk toward public health, regulations are becoming increasingly strict and classical treatments like biological treatments are not efficient. Other techniques such as incineration, oxidation or adsorption provide higher levels of removal but with a high energy and capital cost. A coupled process involving adsorption and oxidation is studied. Four adsorbents are tested and compared according to two objectives, their adsorption capacity and their capability to decompose ozone into powerful hydroxyl radicals. Two model compounds were chosen: 2,4-dichlorophenol and nitrobenzene. Experimental results allow comparing coupled process with results obtained during ozonation alone. Zeolite (Faujasite Y) gave disappointing results in term of both adsorption kinetics and ozone decomposition. On the contrary, activated carbons showed fast adsorptions and important capabilites to decompose ozone into radicals, almost in nitrobenzene experiments. S-23 activated carbon proved to be the most interesting adsorbent for better mechanical and chemical stabilities over time. Sequential adsorption/ozonation experiments were conducted, showing a strong loss of adsorption efficiency after the first operation, but the positive point is that the adsorption capacity remains almost constant during further cycles.

Ozonation of azo dye in a semi-batch reactor: a determination of the molecular and radical contributions.

Azo dye ozonation was carried in a semi-batch reactor to evaluate both the molecular and radical contributions of ozone on the dye decay. From two mass balance equations, the simultaneous determination of mass transfer, self-decomposition and solubility parameters of ozone were determined; thus establishing the steady state conditions in the experimental system. The results of kinetic studies showed that the decay of azo dye was a pseudo-first-order reaction with respect to dye concentration and the overall rate constant increased with an increase in the pH, however declined with an increase in the dye concentration. Furthermore, from the overall rate constants obtained at various pH values a mathematical analysis of dye decay was performed, which provides a practical new method to quantify the radical and molecular contributions in the ozonation of azo dyes.

Removal of nitrogenous compounds by catalytic wet air oxidation. Kinetic study.

Aqueous wastes containing organic pollutants can be efficiently treated by wet air oxidation (WAO), i.e. oxidation by molecular oxygen in the liquid phase, under high temperature (200-325 degrees C) and pressure (up to 150 bar). However, organic nitrogen can be relatively resistant to oxidation and can be harmful to the environment. In the course of treatment, organic nitrogen (N-Org) is converted into ammonia (NH(3)), while organic carbon (C-Org) is converted mainly into carbon dioxide (CO(2)). This can be done without catalysts. In the presence of Mn/Ce composite oxides, it is possible to transform ammonia into molecular nitrogen at a temperature close to 260 degrees C. The direct conversion of organic nitrogen into molecular nitrogen also can be achieved using the same catalyst. This paper discusses the results obtained during the treatment of nitrogenous compounds like aniline, nitrophenol, beta-alanine and ammonia. Laboratory investigations were conducted in a stirred batch reactor with Mn/Ce composite oxides as catalysts. Very limited amounts of nitrites and nitrates were observed with amines, but more significant quantities were found with nitro-compounds. The kinetics of oxidation of ammonia, organic compounds, and more particularly aniline, were investigated. The treatment of a real waste (process wastewater) was also investigated. The dependence of the transformation rate on various parameters (amount of catalyst, temperature, etc.) was established. The rates of oxidation are described by first-order kinetic laws with respect to the various nitrogen species (aniline, NH(3)). Several parallel pathways are considered for the transformation of organic nitrogen, amongst which is an interaction with the catalyst surface. The orders with respect to oxygen and catalyst are established.

Treatment of organic aqueous wastes: Wet air oxidation and Wet Peroxide Oxidation.

There is growing concern about the problems of waste elimination. We should consider our environment as being borrowed from future generations and refrain from leaving a legacy of problems we are not able to solve. Various oxidation techniques are suited for the elimination of organic aqueous wastes, but because of the environmental drawbacks of incineration, enclosed processes, like liquid phase oxidation should be preferred. Wet air oxidation (WAO) under high temperature (200-325 degrees C) and pressure (50-150 bar) is suited to such liquid wastes and various catalysts, including hydrogen peroxide, can be used in order to increase the efficiency without increasing temperature and pressure. Wet Peroxide Oxidation (WPO) is a similar process. A comparable oxidation efficiency is obtained when using hydrogen peroxide as the oxidising agent instead of oxygen, at a temperature of only 100-120 degrees C. As opposed to WAO, which is capital intensive, WPO needs limited capital but generates higher running costs. The paper reviews the major results obtained for both processes and assesses the field of possible application of each of them. TOC removal efficiencies typically obtained range from 65 to 90% or more for most of the pollutants.

Taking mass transfer limitation into account during ozonation of pollutants reacting fairly quickly.

Various situations observed when oxidizing organic compounds via ozone in a semi-batch reactor are illustrated. The resistance to the transfer of ozone from gas to liquid is accounted for using the film model. The mass balances are numerically solved simultaneously within the reactor and within the film to produce time dependent profiles of concentrations, Hatta, enhancement and depletion factors. Firstly, theoretical profiles are exemplified for various kinetic regimes from slow to fast; reaction occurs either in the bulk, in the film or in both. This shows the drastic importance of the shapes of the gas concentration profiles both at the exit of the reactor and in the liquid phase - in determining the regime. Then, a typical example dealing with fumaric acid ozonation is shown. Firstly, the acid itself oxidizes rapidly producing an intermediate regime: part of the reaction occurs within the film, part within the bulk and the rate constant can be determined. Then, the by-products oxidize more slowly producing a typical regime: reaction occurs within the bulk, the concentration of dissolved ozone is almost 0 and the mass transfer coefficient can be determined. Finally, when all organics have oxidized, the self-decomposition of ozone governs a slow kinetic regime: the concentration of dissolved ozone is close to equilibrium.

Wet oxidation of domestic sludge and process integration: the Mineralis process.

Wet oxidation (WO) in subcritical conditions is a new alternative to usual routes for sewage sludge treatment that complies with environmental standards. This paper presents tests carried out using a batch reactor and continuous pilot and industrial units, treating municipal sewage sludge. The main products after oxidation are CO2, water, VFA and ammonia. The results highlight the considerable influence of the treatment temperature and of the type of sewage sludge which is treated. At temperatures around 240 degrees C, VFA fraction present in WO supernatant is limited to 50% because of the presence of non-degraded fatty compounds and surfactants. Moreover, the COD reduction is limited to 70%. On the contrary, at 300 degrees C, COD removal efficiencies greater than 80% are achieved without any catalyst addition and, in addition, only highly biodegradable compounds remain in the oxidised liquor. In order to treat the residual ammonia nitrogen by biological processes, it is therefore necessary to obtain a VFA fraction as high as possible for achieving denitrification and then to operate the WO process at high temperature and without catalyst addition.

Subcritical wet oxidation of municipal sewage sludge: comparison of batch and continuous experiments.

Wet oxidation in subcritical conditions is a new alternative to usual routes for sewage sludge treatment and it complies with environmental standards. The paper presents tests carried out on a batch reactor and on a continuous pilot unit, treating municipal sewage sludge. A method is proposed that shows that the oxidation efficiency in a continuous reactor can only be easily predicted from the residence time distribution and batch tests results. Nevertheless, a partial settling of the solid residue in the continuous bubble column reactor is evident, and it increases the solid residence time and then decreases its organic content with respect to a similar batch test. In addition, these results highlight the considerable influence of temperature in the oxidation reactor and of the type of sewage sludge which is treated. At temperatures around 240 degrees C, foaming can seriously impair the operation of the continuous reactor, because of the presence of non-degraded fatty compounds and surfactants. Moreover, the COD reduction is limited to 70%. On the contrary, at 300 degrees C, COD removal efficiency greater than 80% is achieved without any catalyst additive and, in addition, only highly biodegradable compounds remain in the oxidised liquor.

Oxidation pathways for ozonation of azo dyes in a semi-batch reactor: a kinetic parameters approach.

In this study ozone and the H2O2/O3 oxidation system are used to decolorize aqueous solutions of Orange II (Or-II) and Acid Red 27 (AR-27). Investigations are carried out in a semi-batch bubble column reactor. A system of series-parallel reactions is proposed to describe the mechanism of dye oxidation. The stoichiometric ratio for the first reaction is found to be 1 mol dye per mol O3, while the overall ozone demand for both reactions one and two is found to be 5 and 6 moles for Or-II and AR-27 respectively. Molecular and radical kinetics are compared: a radical scavenger, t-butanol, can be added to ensure only the molecular reaction of ozone, or hydrogen peroxide can be supplied through a peristaltic pump, to initiate radical reactivity. Results reveal that colour removal is ensured by direct ozone attack. For both dyes, TOC removal efficiencies of 50 - 60 % are obtained by the action of the hydroxyl free radical. However, this is not improved by addition of H2O2, thus demonstrating that organic species alone ensure HO degrees radical production during ozonation. Both the mass transfer and the ozone reactivity with the dyes are considered to evaluate the kinetic parameters for the molecular pathway.