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 (kLa) and decomposition rate constant (kC) were determined for each configuration. In presence of solid, kLa was 2.0 to 2.6 times higher and kC 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

Adsorption of Nitrobenzene from Water onto High Silica Zeolites and Regeneration by Ozone

This work investigates the removal of nitrobenzene (NB), a model pollutant from water, by combining adsorption onto zeolites and regeneration with ozone. The adsorption equilibrium isotherms of NB onto zeolites enabled the best adsorbent to be selected and zeolites with a high Si/Al ratio were the most efficient. The adsorption capacity depended on the Si/Al ratio and on the pore size. In a sequential process coupling adsorption and oxidation by ozone, NB was completely removed from water and the initial adsorption capacity of the zeolite was totally restored. Although no catalytic effect was noticed, the adsorption produced locally high concentrations, thus enhancing the oxidation rate for NB

The use of ozone and high silica zeolites to enhance refractory compounds removal

This work investigates the removal of organic pollutants from water through a three-phase process combining adsorption onto hydrophobic zeolites and in situ oxidation by ozone gas. Zeolites are aluminosilicates with various crystalline structures – and especially different pore sizes - which offer a great selectivity, profitable to organic pollutants separation in a complex matrix like natural water. They are highly resistant to chemical agents as acids, bases or oxidising agents such as ozone. Moreover, high silica zeolites have a high adsorption capacity for organics. Ozone is known to be a powerful oxidising agent able to react with various organic compounds. Its action – either direct or indirect - leads to the decomposition of organics into smaller molecules that are generally biodegradable. Previous studies have shown that organics adsorbed onto zeolites could be oxidised by ozonated water faster than in bulk water because of a micropore concentration effect (Fujita et al, 2004 and Sagehashi et al, 2005). In the gas phase, Monneyron et al (2003) showed that high silica zeolites could catalyse ozone decomposition into radical species and that adsorption properties were not significantly modified after exposition to ozone. Hence it is expected that zeolites saturated with organics could undergo regeneration by ozone without degradation of their structures or decrease of their adsorption capacities. The present work showed that high silica zeolites could efficiently adsorb nitrobenzene from water although their capacity stayed beyond that of activated carbon, except at low concentrations. The adsorption capacity depended on the zeolite structure and the Si/Al ratio. Adsorption isotherms could be well described by Langmuir or Freundlich models. As regards the three phase coupled process, the adsorbent could be efficiently regenerated during an ozonation step consisting in bubbling ozone through a suspension of saturated zeolite in a nitrobenzene solution at equilibrium. The initial adsorption capacity was quickly recovered and, continuing the treatment, the adsorption capacity of the zeolite was even increased. This may be due to the cleaning of zeolites pores by ozone (Pic et al, 2005). Yet traces of template molecules could probably remain from the zeolite synthesis process. Until now the catalytic effect of the zeolites has not been evidenced in the liquid phase. Therefore future work will focus on the conditions in which the oxidation kinetics can be enhanced in the presence of zeolites through a concentration effect, and to what extent

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

Coupled selective adsorption and ozonation for non biodegradable COD removal

This paper investigates a new water treatment process based on the combined use of the pollutant adsorption onto a mineral surface, and the ozonation of the adsorbed species. Dioxane has been chosen as a model compound as it is refractory towards ozone alone, and two adsorbents (a high silica zeolite FAU and a mesoporous material M) are tested. Three sets of experiments are shown: pollutant adsorption alone, pollutant ozonation alone and the coupled adsorption/ozonation process. The first results show that FAU is not a well suited adsorbent, as dioxane adsorption itself is weak and, moreover, the coupled process does not induce any benefit. On the other hand, mesoporous material M gives better results, since dioxane removal has been achieved up to 50%. The difference between the two materials is attributed to their catalytic effect: whereas FAU does not react with ozone, M probably decomposes the oxidant, generating free radical species and thus acting as an advanced oxidation process

Influence of activated carbons on the kinetics and mechanisms of aromatic molecules ozonation

Companies have been looking for new methods for treating toxic or refractory wastewaters; which can mainly be used prior to or after or in connexion with biological treatment processes.This paper compares conventional ozone oxidation with activatedcarbon (AC) promoted ozone oxidation, which helps developing a mechanism involving HOradical dot radical. For a compound which is quite easy to oxidise, like 2,4-dichlorophenol (2,4-DCP) conventional ozonation is efficient enough to remove the initial molecule. The mechanism involved mainly consists of an electrophilic attack on the aromatic ring, which is activated by the donor effect of the –OH group, then followed by a 1,3 dipolar cycloaddition (Criegee mechanism) that leads to aliphatic species, mainly carboxylic acids. Yet, the addition of AC, through the presence of HOradical dot radical, enhances the removal of these species which are more refractory.For a refractory compound like nitrobenzene (NB), with a de-activatedaromatic ring because of the attractive effect of –NO2, conventional ozonation is inefficient. On the contrary, this molecule can be quite easily removed with AC promoted oxidation and it is found that the mechanism (electrophilic attack followed by a 1,3 dipolar cycloaddition) is quite similar to the one corresponding to conventional ozonation, but with less selectivity.For both molecules, a mass balance has established that the by-products accounting for more than 75% of the remaining COD can be quantified. A significant part is composed of carboxylic acids (acetic, oxalic, etc.), which could afterwards be easily removed in an industrial wastewater treatment process followed by a final biological treatment step

Land Allocation between Food and Energy

International audienceMany countries are promoting biofuels as a substitute for scarce oil. This paper develops a dynamic model of land allocation between food and energy and shows how the model can be calibrated using standard optimization techniques. Some possible implications of the trade-offs between food and energy are discussed. Specifically, we show that the effect of mandates is mainly felt through increased land conversion, which increases indirect carbon emissions. Crude oil prices do not decrease significantly because of leakages