Carbonaceous materials from a petrol primary oily sludge: Synthesis and catalytic performance in the wet air oxidation of a spent caustic effluent.

Oil refineries produce annually large quantities of oily sludge and non-biodegradable wastewater during petroleum refining that require adequate management to minimize its environmental impact. The fraction solid of the oily sludge accounts for 25 wt% and without treatment for their valorization. This work is focused on the valorization of these solid particles through their transformation into porous materials with enhanced properties and with potential application in the catalytic wet air oxidation (CWAO) of a non-biodegradable spent caustic refinery wastewater. Hence, dealing with the valorization and treatment of both refinery wastes in a circular approach aligned with the petrol refinery transformations by 2050. The obtained oily sludge carbonaceous materials showed improved surface area (260-762 m2/g) and a high Fe content. The good catalytic performance of these materials in CWAO processes has been attributed to the simultaneous presence of surface basic sites and iron species. Those materials with higher content of Fe and basic sites yielded the highest degradation of organic compounds present in the spent caustic refinery wastewater. In particular, the best-performing material ACT-NP 1.1 (non-preoxidated and thermically treated with 1:1 mass ratio KOH:solid) showed a chemical oxygen demand (COD) removal of 60 % after 3 h of reaction and with a higher degradation rate than that achieved with thermal oxidation without catalyst (WAO) and that using an iron-free commercial activated carbon. Moreover, the biodegradability of the treated wastewater increased up to 80% (from ca. 31% initially of the untreated effluent). Finally, this material was reused up to three catalytic cycles without losing metal species and keeping the catalytic performance.

Kinetics and mechanism study of dyes degradation in electric field-promoting catalytic wet air oxidation process.

Wet air oxidation (WAO) is a clean and eco-friendly technology for dyes removal, but the high operating temperature and pressure limit its practical application. In the present work, an electric field-promoting (EF-promoting) catalytic WAO process is developed to degrade dyes under room condition. The oxidation kinetics of four different types of dyes and their degradation pathways are studied. A kinetic model is constructed by including the exogenous electric field into the Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism framework, and quantitative structure-activity relationship (QSAR) analysis is conducted to correlate the kinetic parameters to the physicochemical properties of the dyes. A negative linear relationship is found between the adsorption equilibrium constants of the dyes and their first ionization energies, and their surface reaction rate constants are positively linearly associated to Esum (ELUMO + EHOMO). The degradation pathways of the different dyes are proposed according to the degradation intermediates and the activities of the atoms within the dye molecules. The heteroatoms N and S, and the atom C connecting the aromatic rings are identified as the susceptible sites upon the electrophilic attack of O2. Bond cleavage at these sites gives rise to aromatic fragments which are eventually mineralized via carboxyl acids. The results of this work is helpful for guiding the design and operation of the EF-promoting catalytic WAO process into the treatment of various dye wastewaters.

Use of catalytic wet air oxidation (CWAO) for pretreatment of high-salinity high-organic wastewater.

Catalytic wet air oxidation (CWAO) coupled desalination technology provides a possibility for the effective and economic degradation of high salinity and high organic wastewater. Chloride widely occurs in natural and wastewaters, and its high content jeopardizes the efficacy of Advanced oxidation process (AOPs). Thus, a novel chlorine ion resistant catalyst B-site Ru doped LaFe1-xRuxO3-δ in CWAO treatment of chlorine ion wastewater was examined. Especially, LaFe0.85Ru0.15O3-δ was 45.5% better than that of the 6%RuO2@TiO2 (commercial carrier) on total organic carbon (TOC) removal. Also, doped catalysts LaFe1-xRuxO3-δ showed better activity than supported catalysts RuO2@LaFeO3 and RuO2@TiO2 with the same Ru content. Moreover, LaFe0.85Ru0.15O3-δ has novel chlorine ion resistance no matter the concentration of Cl- and no Ru dissolves after the reaction. X-ray diffraction (XRD) refinement, X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and X-ray absorption fine structure (XAFS) measurements verified the structure of LaFe0.85Ru0.15O3-δ. Kinetic data and density functional theory (DFT) proved that Fe is the site of acetic acid oxidation and adsorption of chloride ions. The existence of Fe in LaFe0.85Ru0.15O3-δ could adsorb chlorine ion (catalytic activity inhibitor), which can protect the Ru site and other active oxygen species to exert catalytic activity. This work is essential for the development of chloride-resistant catalyst in CWAO.

A comparative study among catalytic wet air oxidation, Fenton, and Photo-Fenton technologies for the on-site treatment of hospital wastewater.

The feasibility of catalytic wet air oxidation, intensified homogeneous Fenton and heterogeneous Photo-Fenton systems for the treatment of real hospital wastewater has been investigated. Wastewater samples were collected from a hospital sewer, during a weekly monitoring program, and fully characterized. Up to seventy-nine pharmaceuticals, including mostly parent compounds and some of their transformation products, were analyzed. Catalytic wet air oxidation allowed the complete removal of several pharmaceutical groups, but it did not allow to eliminate analgesics/anti-inflammatories and antibiotics, whose average removal was around 85%. Intensified Fenton oxidation was the most efficient process for all the drugs removal with an almost complete reduction of the initial pharmaceutical load (99.8%). The heterogeneous Photo-Fenton system reached a 94.5% reduction of the initial pharmaceutical load. The environmental risk of the treated samples by the hazard quotient (HQ) method was also evaluated. Fenton oxidation was the most effective system with a final ∑HQ of 5.4. Catalytic wet air oxidation and Photo-Fenton systems achieved total ∑HQ values of 895 and 88, respectively. This fact was related to the presence of refractory antibiotics in the treated catalytic wet air oxidation samples. On the opposite, the Photo-Fenton system provided the elimination of most pharmaceutical pollutants that pose a high environmental risk such as antibiotics. Simplified cost estimation was finally performed as a preliminary approach of the economy of the three oxidation processes for the hospital wastewater treatment.

Aqueous phase reforming coupled to catalytic wet air oxidation for the removal and valorisation of phenolic compounds in wastewater.

Aqueous phase reforming (APR) coupled to catalytic wet air oxidation (CWAO) has been investigated as an approach to remove phenolic compounds from wastewater, converting them into valuable gases. Partial oxidation of phenol was achieved in the first CWAO stage trying to minimize mineralization so to allow a high yield to valuable gases in the second APR stage. APR runs were carried out with different mixtures of compounds corresponding to phenol oxidation pathway (phenol, quinones, long and short chain acids) and representing different degrees of oxidation in CWAO stage. A range of TOC and COD removal (74-90%) was observed in APR stage for the single compounds, with higher removal for long chain acids. Likewise, long chain acids provided with the highest conversion to gases. APR of mixtures rich in acids gave the highest yield to CH4 (11.0 mmol CH4/g TOCinitial). H2 production was low in all cases, due to competing direct conversion of long and short chain acids into CH4. TOC and COD removal from wastewater was similar in APR-CWAO and APR, however the conversion to gases and the yield to CH4 were markedly higher for APR-CWAO, thus overcoming the difficulties previously observed in the direct APR of phenol.

Bioinspired metal oxide particles as efficient wet air oxidation and photocatalytic oxidation catalysts for the degradation of acetaminophen in aqueous phase.

The catalytic performances of the biomimetic metal oxides were tested in photo Fenton-like oxidation and catalytic wet air oxidation processes. Biomimetic copper oxide, iron oxide, and cobalt oxide catalysts were prepared by using pollen grains as biotemplate. The surface characteristics of the biomimetic metal oxides were characterized. SEM micrographs of the biomimetic catalysts demonstrated that pollen grains were successfully mimicked by metal oxide structures. The influences of UV light intensity, catalyst loading, and the initial hydrogen peroxide concentration on acetaminophen degradation were investigated in the photo Fenton-like oxidation process whereas the effects of reaction temperature and catalyst loading were investigated in catalytic wet air oxidation process. The biomimetic copper oxide was the most effective catalyst for the removal of acetaminophen in both of the advanced oxidation processes. The highest acetaminophen degradation efficiency was 86.9% in photo Fenton-like oxidation process when the initial acetaminophen concentration, catalyst loading, and the initial H2O2 concentrations were 10 mg/L, 0.1 g/L and 1 mM, respectively, at room temperature. In the catalytic wet air oxidation process, 98.3% degradation was achieved for the treatment of 100 mg/L acetaminophen solutions at 180 °C and 10 bar by using 1 g/L of catalyst loading at the same reaction time as photo Fenton-like oxidation. Mineralization analysis and the toxicity tests indicated that the biomimetic copper oxide catalysts were promising for the acetaminophen removal in catalytic wet air oxidation processes.

Wet air oxidation of cresylic spent caustic - A model compound study over graphene oxide (GO) and ruthenium/GO catalysts.

Wet air oxidation (WAO) is a candidate technique for the effective treatment of spent caustic wastewater. In this work, cresols were chosen as model compounds to represent cresylic spent caustic wash. Graphene oxide (GO) is a promising catalyst as well as support for the wet oxidation process, due to its unique structure and properties. For the first time, GO and ruthenium supported on graphene oxide (Ru/GO) were employed for WAO of cresylic isomers. The aforesaid materials were synthesized by modified Hummer's method and characterized using scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analysis. The performance of the investigated materials for WAO of cresols was studied in a slurry reactor. The best reaction conditions for GO were 175 °C and 0.69 MPa O2 pressure. Total organic carbon (TOC) degradation achieved at these conditions was 54.9, 48.9 and 61.2% for o-cresol, m-cresol and p-cresol, respectively. The amount of TOC degradation obtained by using Ru/GO at the same reaction conditions was 66.4, 53.4 and 73.9% for o-cresol, m-cresol and p-cresol, respectively. It was found that the order of reactivity for cresols was p-cresol > o-cresol > m-cresol. Finally, kinetics of TOC destruction during CWAO of p-cresol over GO was described using a two-step power law model.

Performance of various catalysts on treatment of refractory pollutants in industrial wastewater by catalytic wet air oxidation: A review.

The tremendous increase of industrialization and urbanization worldwide causes the depletion of natural resources such as water and air which urges the necessity to follow the environmental sustainability across the globe. This requires eco-friendly and economical technologies for depollution of wastewater and gases or zero emission approach. Therefore, in this context the treatment and reuse of wastewater is an environmental friendly approach due to shortage of fresh water. Catalytic wet air oxidation (CWAO) is a promising technology for the treatment of toxic and non-biodegradable organic pollutants in the wastewater generated from various industries. Various heterogeneous catalysts have been extensively used for treatment of various model pollutants such as phenols, carboxylic acids, nitrogenous compounds and different types of industrial effluents. The present review focuses on the literature published on the performances of various noble and non-noble metal catalysts for the treatment of various pollutants by CWAO. Reports on biodegradability enhancement of industrial wastewater containing toxic contaminants by CWAO are reviewed. Detailed discussion is made on catalyst deactivation and their mitigation study and also on the various factors which affects the CWAO reaction.

Degradation of phenylamine by catalytic wet air oxidation using metal catalysts with modified supports.

The effect of acid treatments with HCl and HNO3 on the surface area and surface chemistry of three granular activated carbons was studied. These supports were characterized and the hydrochloric acid treatment leads to the best activated carbon support (AC2-C). The catalytic behavior of Pt, Ru and Fe (1 wt.%) supported on granular activated carbon treated with HCl was tested in the phenylamine continuous catalytic wet air oxidation in a three-phase, high-pressure catalytic reactor over a range of reaction temperatures 130-170ºC and total pressure of 1.0-3.0 MPa at LHSV = 0.4-1 h(-1), whereas the phenylamine concentration range and the catalyst loading were 5-16 mol.m(-3) and 0.5-1.5 g, respectively. Activity as well as conversion varied as a function of the metal, the catalyst preparation method and operation conditions. Higher activities were obtained with Pt incorporated on hydrochloric acid -treated activated carbon by the ion exchange method. In steady state, approximately 98% phenylamine conversion, 77% of TOC and 94% of COD removal, was recorded at 150ºC, 11 mol m(-3) of phenylamine concentration and 1.5 g of catalyst, and the selectivity to non-organic compounds was 78%. Several reaction intermediaries were detected. A Langmuir-Hinshelwood model gave an excellent fit of the kinetic data of phenylamine continuous catalytic wet air oxidation over the catalysts of this work.

Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.

The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable.

Optimization of catalytic wet air oxidation process in microchannel reactor for TBBS wastewater treatment.

Catalytic wet air oxidation (CWAO) process is employed for the treatment of N-tert-butyl-2-benzothiazolesulfenamide (TBBS) wastewater in a microchannel reactor that enables continuous operation of the reaction and allows for thorough mixing of oxygen and pollutants. To achieve the optimal process performance, four key parameters of pressure, temperature, time, and the mass ratio of input oxygen to wastewater COD are optimized using both response surface methodology (RSM) and backpropagation artificial neural network (BP-ANN). According to the correlation coefficients of model results and experimental data, BP-ANN performs better than RSM in simulation and prediction. The analysis of variance in RSM shows that all parameters are significant for the obtained quadratic model, but their interactions with each other are not significant. Connection weights algorithm is used to determine the relative importance of these parameters for the process efficiency, and it is demonstrated that temperature is the most influential parameter with a relative importance of 35.61%, followed by pressure (29.74%), time (19.53%) and ROC (15.12%).

Effect of inorganic salt on the removal of typical pollutants in wastewater by RuO2/TiO2 via catalytic wet air oxidation.

The treatment of high-salinity and high-organic wastewater is a tough task, with the removal of organic matter and the separation of salts often mutually restricting. Catalytic wet air oxidation (CWAO) coupled desalination technology (membrane distillation (MD), membrane bioreactor (MBR), ultrafiltration (UF), nanofiltration (NF), etc.) provides an effective method to simultaneously degrade the high-salinity (via desalination) and high-organic matters (via CWAO) in wastewater. In this work, five kinds of RuO2/TiO2 catalysts with different calcination temperatures were prepared for CWAO of maleic acid wastewater with a theoretical chemical oxygen demand (COD) value of 20,000 mg L-1. RuO2/TiO2 series catalysts demonstrated prominent salt resistance, with more than 80% TOC removal rates in the CWAO system containing 5 wt% Na2SO4; while RuO2/TiO2-350 showed the best degradation performance in both non-salinity and Na2SO4-containing conditions. Multiple characterization techniques, such as XRD, BET, XPS, NH3-TPD and TEM etc., verified the physicochemical structure of RuO2/TiO2 catalysts, and their influence on the degradation of pollutants. The calcination temperature was found to have a direct impact on the specific surface area, pore volume, oxygen vacancies and acid sites of catalysts, which in turn affected the ultimate catalytic activity. Furthermore, we also investigated the performance of the RuO2/TiO2-350 catalyst for the treatment of acids, alcohols and aromatic compounds with the addition of NaCl or Na2SO4, proving its good universality and excellent salt resistance in saline wastewater. Meanwhile, the relationship between the structure of three types of organic compounds and the degradation effect in the CWAO system was also explored.

Catalytic wet air oxidation of toxic containments over highly dispersed Cu(II)/Cu(I)-N species in the framework of g-C3N4.

Catalytic wet air oxidation (CWAO) is a harmless, cheap and effective technology for the degradation of toxic containments directly to CO2 and H2O. In this work, highly dispersed Cu(II)/Cu(I)-N that embedded in the framework of g-C3N4 (Cux-g-C3N4) were synthesized in a facile thermal polymerization method and used in the CWAO of phenols, antibiotics and vitamins. Characterization results confirmed that g-C3N4 formed in the prepared catalyst and copper was chemically coordinated with N in g-C3N4, which inhibited the aggregation of copper. Meanwhile, Cu(II) or Cu(I) in the framework of g-C3N4 was more effective for the degradation of phenol than Cu(0) and CuO, and more than 23 toxic containments could be degraded under mild conditions. The prominent performance of Cu0.1-g-C3N4 for CWAO reaction was discussed on the base of these experiments and it was disclosed that in-situ formed H2O2 might be contributed to the highly activity.

Enhancing electronic metal support interaction (EMSI) over Pt/TiO2 for efficient catalytic wet air oxidation of phenol in wastewater.

Phenol is one of the major hazardous organic compounds in industrial wastewater. In this work, a highly active Pt/TiO2 catalyst for catalytic wet air oxidation (CWAO) of phenol was obtained by supporting pre-synthesized Pt on TiO2. During the followed hydrogen reduction, strong hydrogen spillover occurred without the migration of TiO2 onto Pt. The reduced support then enhanced the electron transfer from TiO2 to Pt, increasing the percentage of partially negative Pt (Ptδ-), which has been confirmed by XPS. The strong EMSI made the obtained catalyst far more active than Pt/TiO2 prepared by impregnation method. The electron-enriched Pt/TiO2 achieved total organic carbon (TOC) conversion of 88.8% and TOF 149 h-1 at 100 °C and 2 MPa O2, while conventional Pt/TiO2 gave TOC conversion of 39.5% and TOF 41 h-1 for CWAO of phenol. Our work indicates that the enhancement of EMSI between metal and support can be an effective approach to develop highly active catalysts for phenol treatment.

A New Route for Low Pressure and Temperature CWAO: A PtRu/MoS2_Hyper-Crosslinked Nanocomposite.

PtRu/MoS2 nanoparticles (NPs) (PtRu alloy partially coated by one-layer MoS2 nanosheets) were prepared through a 'wet chemistry' approach. The obtained NPs were directly embedded, at 5 parts per hundred resin/rubber (phr) loading, in a poly (divinylbenzene-co-vinyl benzyl chloride) hyper-crosslinked (HCL) resin, synthesized via bulk polymerization of the resin precursors, followed by conventional FeCl3 post-crosslinking. The obtained HCL nanocomposites were characterized to evaluate the effect of the NPs. It shows a high degree of crosslinking, a good dispersion of NPs and a surface area up to 1870 ± 20 m2/g. The catalytic activity of the HCL nanocomposite on phenol wet air oxidation was tested at low air pressure (Pair = 0.3 MPa) and temperature (T = 95 °C), and at different phenol concentrations. At the lower phenol concentration, the nanocomposite gives a total organic carbon (TOC) conversion of 97.1%, with a mineralization degree of 96.8%. At higher phenol concentrations, a phenol removal of 99.9%, after 420 min, was achieved, indicating a quasi-complete depletion of phenol, with a TOC conversion of 86.5%, corresponding to a mineralization degree of 84.2%. Catalyst fouling was evaluated, showing good reusability of the obtained nanocomposite.

Electro-activation of O2 on MnO2/graphite felt for efficient oxidation of water contaminants under room condition.

The activation of oxygen (O2) under room condition is highly desirable for oxidative removal of organic pollutants in water. Herein, we report a graphite felt (GF)-supported α-MnO2 catalyst which is active for activating O2 with assistance of an anodic electric field. The electro-assisted catalytic wet air oxidation (ECWAO) process on MnO2/GF is able to rapidly degrade a variety of dyes, pharmaceutics and personal care products (PPCPs) under room condition. The congo red, basic fuchsin, neutral red and methylene blue are completely mineralized in 160 min, and the bisphenol A, triclosan and ciprofloxacin are mineralized by 89.9%, 81.5% and 65.4%, respectively, in 300 min. Mechanistic study indicates a surface-catalyzed non-free radical pathway for the oxidation of organic pollutants by O2 in the ECWAO process. The oxygen vacancies on MnO2 are identified as the catalytically active sites, at which oxygen atom is transferred from O2 to organic molecule through chemisorbed oxygen species. The anodic electric field assists such an oxygen transfer pathway by activating the complex of chemisorbed oxygen species and organic molecule through electro-oxidation reaction. The ECWAO process on MnO2/GF electrode exhibits a great potential for practical wastewater treatment under room condition.

Catalytic Liquid-Phase Oxidation of Phenolic Compounds Using Ceria-Zirconia Based Catalysts.

Catalytic liquid-phase oxidation using a catalyst and oxygen gas (Catalytic wet air oxidation, CWAO) is one of the most promising technology to remove hazardous organic compounds in wastewater. Up to now, various heterogeneous catalysts have been reported for phenolic compounds decomposition. The CeO2-ZrO2 based catalysts have been recently studied, because CeO2-ZrO2 works as a promoter which supplies active oxygen species from inside the lattice to the active sites. Since it is difficult to dissolve oxygen gas into water, the use of the promoter is effective for realizing the high catalytic activity at moderate conditions. Also, CeO2-ZrO2 shows high resistance for the metal leaching during the catalytic reaction in the liquid-phase. This article reviews the studies of the catalytic liquid-phase oxidation of phenolic compounds using CeO2-ZrO2 based catalysts.

Catalytic wet air oxidation of Reactive Black 5 in the presence of LaNiO3 perovskite catalyst as a green process for azo dye removal.

The removal of textile azo dye, Reactive Black from the aqueous solutions by catalytic wet air oxidation in the presence of LaNiO3 perovskite catalyst has been investigated. The most suitable reaction conditions were determined by testing various the catalyst loadings, reaction temperature and pressure values, and the initial pH of the Reactive Black 5 solutions. The most suitable reaction conditions with 0.61 L/min of air flow rate were found to be 1 g/L of LaNiO3 loading, 50 °C of reaction temperature, 1 atm of reaction pressure, and, pH = 3 for the oxidation of 100 mg/L Reactive Black solutions. Under these conditions the degradation and the decolorization efficiencies were evaluated as 65.4% and 89.6%, respectively. The phytotoxicity analyzes were carried out by using Lepidium sativum. According to the toxicity tests a remarkable decrease in the growth inhibition was achieved by the catalytic wet air oxidation in the presence of LaNiO3 catalyst. The growth inhibition in the untreated and treated dye solutions were calculated as 49.3% and 23.7%, respectively.

Preparation, characterization, and testing of metal-doped carbon xerogels as catalyst for phenol CWAO.

Co-, Ce-, and Ni-doped carbon xerogels (Me-CX) synthesized by sol-gel method followed by an ion exchange process were used as catalysts for catalytic wet air oxidation (CWAO) of phenol. The prepared catalysts were characterized using TEM, SEM, BET surface area, and XRD. Me-CX catalysts were tested in mild conditions (20-60 °C, atmospheric pressure) in a semi-batch reactor in various reaction conditions (30-60 L/h, 0.05-0.2 g catalysts, 50-175 mg phenol/L). Total organic carbon (TOC) removal efficiency values obtained decrease in the following order Co-CX â‰… Ce-CX > Ni1-CX > K-CX for the catalysts obtained using the same procedure. TOC removal efficiencies of up to 72% were reached in case of Co-CX catalyst at 20 °C, 40 L/h, using 0.15 g catalyst and a solution of 100 mg phenol/L.

Carbon and nitrogen removal from glucose-glycine melanoidins solution as a model of distillery wastewater by catalytic wet air oxidation.

Sugarcane molasses distillery wastewater contains melanoidins, which are dark brown recalcitrant nitrogenous polymer compounds. Studies were carried out in batch mode to evaluate Pt and Ru supported catalysts in the Catalytic Wet Air Oxidation (CWAO) process of a synthetic melanoidins solution, prepared by stoichiometric reaction of glucose with glycine. The addition of a catalyst slightly improved TOC removal compared with the non-catalytic reaction, and especially promoted the conversion of ammonium produced from organically-bound nitrogen in melanoidins to molecular nitrogen and nitrate. The selectivity to N2 attained 89% in the presence of the Pt catalysts in the reaction conditions used (TOC=2200mgL(-1), TN=280mgL(-1), 0.5g catalyst loaded with 3% metal, 210°C, 70bar total air pressure). To avoid leaching of the active metal by organically-bound nitrogen, the reaction was very efficiently performed in a two-step reaction consisting in WAO to convert nitrogen into ammonium, before the introduction of a catalyst.