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

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

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

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

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

Oxydation humide des polluants organiques par l'oxygène moléculaire activée par le couple H²O²/Fe²+: Optimisation des paramètres opératoires

L'oxydation humide par l'oxygène moléculaire (procédé WAO) activée par le couple (H202/Fe2+) a été mise en oeuvre pour l'oxydation de la pollution organique aqueuse à travers deux composés modèles: l'acide succinique, normalement oxydable, et l'acide acétique, réputé réfractaire. L'influence des différents facteurs a été étudiée par la planification d'expériences. Après leur recensement, une étape préliminaire de criblage a été menée à bien en utilisant une matrice de Plackett et Burman. Seuls les paramètres les plus influents ont été gardés pour l'étape ultérieure d'établissement de modèles prévisionnels à partir d'une matrice composite centrée orthogonale. Les modèles établis ont été validés et ont permis de déterminer les conditions optimales de fonctionnement. L'effet de la température fait apparaître un optimum, à environ 200 °C, au-delà duquel la décomposition du peroxyde devient trop rapide. L'effet de la quantité de peroxyde d'hydrogène introduit est déterminant et l'ajout de moins de 20 % de la quantité stoechiomé- trique permet d'obtenir à 200 °C, avec environ 10 ppm de sels de fer, une efficacité de traitement d'environ 70% pour un composé normalement oxydable. Dans des conditions analogues, le procédé conventionnel sans promoteur conduit à une efficacité inférieure à 5 %.Wet air oxidation (WAO) is a liquid phase oxidation process using molecular oxygen at high temperature (250-300°C) and high pressure (50-150 bar). It can help treating toxic organic aqueous wastes from chemical industries with efficiencies up to 98% after 1 hour. The process can also help treating sludges from domestic sewage treatment facilities. It is usually very cost effective because of the very high operating pressure.This paper deals with the promoted wet air oxidation of acetic acid, rnodel compound for refractory wastes, and succinic acid, model for readily oxidized wastes. The study was conducted in order to determine the promoting effect when adding small dosages of hydrogen peroxide (with iron salts) during oxidation by molecular oxygen. It was previously shown that the initiating step is very temperature dependent (Reaction I) and limits the overall oxidation process The addition of small amounts of H2O2/Fe2+ (Fenton's reagent) can promote the forrnation of very reactive OH• radicals able to develop R• radicals (Reaction IV), even at a low temperature. Then, the oxidation (Reactions VI and VII) continues using molecular oxygen, but the peroxide should be added continuously during a batch test in order to maintain the initiating step.An optimal design methodology was used in order to assess the dependency of the oxidation effrciency on the various parameters and mainly on the promotors. At frrst, a Plackett and Burman design of experiments (PE1) was used to screen the most important variables among those likely to have an effect. The design of experiments, the conditions of the runs and the results (tables 1 to 3) allowed the determination of a new experimental domain and the selection of the four most important variables for the further design of experiments. At the same time, the effect of an addition of phenol (able to reduce iron to the ferrous species, more efficient) was considered. For succinic acid oxidation, a central composite optimal design (PE2) was used (tables 4 and 5). The results allowed us to establish a predictive model (Relationship lX, table 6 and figure 2) and typical results are presented in figures 3 and 4. Approximately 50% oxidation efficiencies could be obtained at 200°C; without peroxide addition, only 5% efficiency is obtained under similar conditions. Moreover, it was observed that the optimum temperature is around 205°C and that phenol is not compatible with peroxide as a promotor. A third optimal design (PE3) was used to predict the efficiency of the method for the treatrnent of acetic acid, a model for a refractory waste. It is composed only of a fractional factorial design (table 7 and 8) and the bias corresponds to the main quadratic effect of temperature (Relationship XIII and table 10). The optimum temperâture is also 205°C and greater than 20% oxidation efficiencies are obtained; at such a temperature, acetic acid cannot be oxidized with the conventional process.The results obtained for the two model compounds validate this oxidation technique. The addition of about 10 ppm of ferrous iron and of less than 20% of the stoichiometric amount in hydrogen peroxide can turn a high pressure WAO process into a medium pressure one

Comparison of Activated Carbon and Hydrophobic Zeolite Efficiencies in 2,4-Dichlorophenol Advanced Ozonation

This study aims at comparing the removal of 2,4-dichlorophenol (2,4-DCP) by 3 methods; adsorption using hydrophobic zeolite (faujasite) or activated carbon (S-23 and L-27), conventional ozonation and hybrid adsorption/ozonation treatment. On the one hand, the three materials correctly adsorb 2,4-DCP; however the adsorption kinetics using zeolite is very low. On the other hand, ozonation totally removes 2,4-DCP after 1 h experiment and the simultaneous combination of adsorbent and ozone does not change the 2,4-DCP degradation. But, though ozonation and hybrid process appear to be equivalent for 2,4-DCP removal, activated carbons are able to decompose ozone and to improve chemical oxygen demand (COD) removal, whereas the zeolite does not show this catalytic effect. Similar results were also observed in a former study with nitrobenzene. Adsorbent degradation is evaluated by Brunauer, Emmet and Teller (BET) and differential thermogravimetric (DTG) analysis, which evidence that Faujasite and S-23 activated carbon are resistant to ozone exposure whereas the pore volume and the surface area of L-27 activated carbon decrease during ozonation

Oxydation en voie humide de la pollution organique aqueuse par le peroxyde d'hydrogène Procédé « Wet Peroxide Oxidation » (WPO®) Étude de nouveaux catalyseurs

Les effluents aqueux pollués par des matières organiques provenant d'industries chimiques présentent souvent une faible biodégradabilité. Dans certains domaines de concentration (DCO = 0,5 - 15 g/l), le procédé WPO® développé au laboratoire se substitue avantageusement à l'incinération pour traiter ce type d'effluents. La réaction, qui met en œuvre le réactif de Fenton à température élevée, conduit parfois à la formation de quantités importantes d'acides carboxyliques légers. Nous avons donc développé des systèmes catalytiques originaux remplaçant les sels de fer et conduisant à une oxydation totale des acides carboxyliques. Le système le plus efficace constitué de sels de fer, de cuivre et de manganèse permet d'obtenir, en 1 h à 100 °C, l'oxydation totale d'un mélange synthétique de ces acides (COT = 5 g/l) avec 1,5 fois la quantité de peroxyde théoriquement nécessaire à l'oxydation. Le catalyseur précipité et séparé en fin de traitement peut être recyclé et conserve la môme activité. Les unités industrielles permettant d'effectuer le traitement WPO® avec les nouveaux catalyseurs, recyclés ou non, seront similaires à celle déjà réalisée pour le traitement de « points noirs » industriels.There is an important concern about the problems occuring with wastes elimination, specially the industrial liquid wastes. Te face the problem of organic aqueous wastes coming front various branches of industry, the WPO® (wet peroxide oxidation) process was developed at the laboratory. In the WAO process (wet air oxidation), which uses gaseous oxygen, the limiting step is usually oxygen transfer. In this new process, this problem is suppressed by using a liquid oxidising agent (hydrogen peroxide). This process is adapted from the classical Fenton's reaction and iron salts are used as the catalyst in order to promote the formation of •OH radicles which are the main active species. But the reaction is carried out at about 120 °C; so, a very significant TOC (total organic carton) removal efficiency is obtained (60 to 90 %) in comparison with the low efficiency of the classical Fenton's reagent (typically 25 % at room temperature).Significant amounts of free fatty acids are formed during the reaction. They are namely oxalic, malonic, succinic and acetic acids, which are common by products obtained during audition of most industrial organic pollutants. In order to comply with the regulations requirements, it was necessary to improve the efficiency of the original process. It was also very important to obtain an efficient elimination at a temperature not greater than 100 °C in order to avoid to pressurize the treatment reactor. This could be obtained by using new catalysts which are described in this paper.Because of the related field, precious metals like Pt and potentially toxic ones like Cr were not considered. One needs a treatment process as cheap and as reliable as possible. So, only Fe, Cu, Co, Ni and Mn were used as salts in order to test their calalytic activity in the treatment by hydrogen peroxide of a synthetical mixture of oxalic, malonic, succinic and acetic acids (O, M, S, A). The experimental device is a stirred tank reactor where the organics and the catalyst are batch loaded. It is continuously fed, for 1 hour, with hydrogen peroxide. The total amount injected is 1.5 the stoechiometric amount. In table 1, it can be seen that any metal has a satisfactory activity when used alone (TOC removal efficiency cannot exceed 22 %). In table 2, it is clear that, in soma cases, the association of two or three metals with each other can lead to very important synergetic effects. When using a mixture of Fe, Cu and Mn, the removal efficiency can increase to 91 %. This Fe/Cu/Mn catalyst is studied with further details in table 4. It appears to have its best efficiency at about 100 °C because of a parasitic decomposition of the peroxide at higher temperatures. For an organic mixture coutaining 5 g TOC/l, 100 ppm of each metal is a convenient concentration. This new catalyst still needs an acidic pH, from 3 to about 5, but the dependency is not so strict than with Fe alone (original process) which needs a value from 3 to 3.5. In addition, it was observed that the treatment time could be easily reduced (down to 45 minutes) as well as the amount of peroxide injected.Very similar results have been obtained with synthetic solutions of pollutants and with real industrial ones, thus establishing the ability of the Fe/Cu/Mn mixture to catalyse the oxidation of a large variety of species and not only carboxilic acids. The difference between the efficiency of this new catalyst and the conventional one is shown in table 5. Figures 1 and 2 are related to an Industrial WPO® unit which is commonly used with the conventional catalyst (Fe). It has been possible to improve its efficiency by using the new one without any significant modification. The Fe/Cu/Mn catalyst can be easily separated alter reaction (coprecipitation effect). Thus, the treated water meets the regulation requirements and the recovered catalyst can be easily resolubilized and recycled

Traitement avancé de micropolluants organiques dans l'eau par couplage entre adsorption sur charbon actif et ozonation catalysée

Traitement avancé de micropolluants organiques dans l'eau par couplage entre adsorption sur charbon actif et ozonation catalysé