ABSRACT This study was to investigate the removal efficiency and kinetics in oxidation of ammonia solutions (NH3-N) in ranging from 400 mg/L to 1000 mg/L by adding Cu/La/Ce catalyst in process of Wet Air Oxidation (denoted by WAO). All experiments were conducted in semi-batch and continuous reactors in series. The major parameters included temperature, pressure, concentration and pH. In the semi-batch type of WAO experiments, the major parameters were performed at the following conditions: an initial concentration NH3-N of 400 mg/L, temperatures ranging from 423 K to 503 K, a total pressure of 4.0 Mpa, and a pH of 12.0. A removal efficiency of 32.7%was obtained in WAO process at 503 K for180 min, but it could be significantly promote to 95.1% after adding a catalyst of molar ratio 7:2:1.The kinetics of WAO with this catalyst in oxidation of NH3-N solutions, using a test of half-life, was developed nearly to a zero order. The reaction constants were 10.12 KJ/mol, 9.12 KJ/mol, and 6.57 KJ/mol at 503 K, 473 K and 423 K. In the continuous type of WAO experiments, the major parameters were performed at the following conditions: an initial concentration NH3-N of 400 mg/L, a temperature of 503 K, a total pressure of 2.0 Mpa, a pH of 12.0 and a liquid space velocity of 4.5 hr-1 (averagelyresidence time 14 min) . A removal efficiency of NH3-N of 6.5 % only was achieved in WAO process for a space velocity of 4.5 hr-1 (averagely residence time 14 min) , but after adding a catalyst of molar ratio 7:2:1 it increased to 72.3 % for a same residence time and a better efficiency of above 91 % was found for 1.5 hr-1 (averagely residence time 40 min) . For increasing the initial concentration of NH3-N into 600 mg/L, 800 mg/L, and 1000 mg/L the removal efficiency of NH3-N decreased with 85 %,75 % and 69 % for 1.5 hr-1 . Thus, the initial concentration of NH3-N in influent inhibits the removal efficiency in the oxidation process. The higher initial concentration the lower removal efficiency.

Yes / Among several treatment methods Catalytic Wet Air Oxidation (CWAO) treatment is considered as a useful and powerful method for removing phenol from waste waters. In this work, mathematical model of a trickle bed reactor (TBR) undergoing CWAO of phenol is developed and the best kinetic parameters of the relevant reaction are estimated based on experimental data (from the literature) using parameter estimation technique. The validated model is then utilized for further simulation and optimization of the process. Finally, the TBR is scaled up to predict the behavior of CWAO of phenol in industrial reactors. The optimal operating conditions based on maximum conversion and minimum cost in addition to the optimal distribution of the catalyst bed is considered in scaling up and the optimal ratio of the reactor length to reactor diameter is calculated with taking into account the hydrodynamic factors (radial and axial concentration and temperature distribution).

In this study, the wastewater generated from etching process of the Printed Circuit Board (PCB) was treated by a process including both acidification and coagulation/sedimentation and then followed by the catalytic wet air oxidation (CWAO) over different catalysts (either Pt/SiO2¡PAl2O3 or Pt¡PX/£^-Al2O3) process in series. Although the initial chemical oxygen demand (COD) concentration of the wastewater is as high as 7740-12700 mg/L, the effluent of the pretreatment process was measured to have COD value in ranges of 3050-4260 mg/L. Several re-action parameters, such as reaction temperatures (200-260¢J), oxygen partial pressures (0-3 MPa), and two kinds of catalysts were performed experimentally to investigate the COD reduction of the wastewater during the CWAO process. Both reaction temperature and variety of catalyst are found most effectively on the COD reduction. However, the effect of oxygen partial pressure on the COD reduction is just in little. Results showed that the COD reduction during the CWAO over the Pt¡PX/£^-Al2O3 catalyst process is the most significant, which with a tow-step re-action and both the two reactions do obey first-order reaction kinetics. A change from a higher reaction activity of the CWAO reaction to a slower one implies a decrease of the reaction rate. On basis of our experiments data, the effective operating conditions of CWAO for the COD reduction was observed to be at temperature of 260¢J under oxygen partial pressure of 2.0 MPa and at a retention time period of 60 min. The COD conversion was calculated as high as 75%; however, it could be enhanced up to 78% and 91%, respectively, when the CWAO was conducted in presence of the Pt/SiO2¡PAl2O3 and Pt¡PX/£^-Al2O3 catalysts, respectively. It can be seen that the organic compound of the wastewater was mineralized most completely (with a COD/TOC ratio of 3.7¡Ó0.2) after the CWAO over the Pt¡PX/£^-Al2O3 catalyst process. Furthermore, a higher COD/TOC ratio of 3.9¡Ó0.3 was achieved when the Pt/SiO2¡PAl2O3 catalyst was in presence of the CWAO process, and the primitive WAO process had the highest COD/TOC ratio of 4.8¡Ó0.4. The experimental data showed that both a higher reaction temperature (¡Ù260¢J) and an application of catalyst are more important factors for the min-eralization of the organic compound of the wastewater during the CWAO process. In our investigation, BOD5/COD ratio has been used to assess if the WAO and/or the CWAO process treatment yield products more amenable to biodegradation. The BOD5/COD ratio was 0.68-0.93 when the reaction temperature was above 220¢J and the retention time was as long as 60 min. Unfortunately, the BOD5/COD ratio of the effluent from the CWAO process came out a lower value (0.45-0.65) though it was under the same reaction conditions. It is probable that the biodegradable portion of the organic compounds of the wastewater were decomposed easier during the CWAO process than during the WAO process. In addition, it was found that the products of the wastewater was decomposed partially into CO2 and into some low molecular weigh acids, such as formic acid, acetic acid, propionic acid, etc. The activation energy with respect to COD was calculated to be 38.42 kJ/mole and 83 kJ/mole, respectively, for the first-step reaction and for the second-step reaction, respectively, of the WAO process. It was al-so calculated that the first-step reaction of the CWAO over the Pt/SiO2¡PAl2O3 catalyst process has activation energy of 18.25 kJ/mole and 25.76 kJ/mole is for the second-step reaction. However, 16.05 kJ/mole and 49.61 kJ/mole are calculated for the first-step and the sec-ond-step reactions, respectively, of the CWAO over the Pt¡PX/£^-Al2O3 catalyst process. It can be seen that the application of both the Pt/SiO2¡PAl2O3 and the Pt¡PX/£^-Al2O3 catalysts has a significant effect on reducing the activation energy of the WAO. It was observed that the total COD conversion of the wastewater is as high as 96% and the BOD5/COD ratio of the effluent has been en-hanced up to more than 0.6. The combination of both the CWAO over the Pt¡PX/£^-Al2O3 catalyst and the biological treatment is a promising tech-nique for the PCB¡¦s wastewater treatment to fit the wastewater control regulation in Taiwan, which requests the COD value of the wastewater discharged should be less than 120 mg/L.

Des catalyseurs hétérogènes à base d'oxydes de manganèse associés aux dioxydes de titane, zirconium et cérium (Mn-Ti-O, Mn-Zr-O et Mn-Ce-O) ont été préparés par différentes voies de synthèse et évalués dans l'Oxydation en Voie Humide Catalytique (OVHC) de la méthylamine. Diverses voies de synthèse ont été explorées pour la préparation de ces catalyseurs, notamment une voie sol-gel mettant en oeuvre des copolymères à bloc, une voie de nanomoulage dans des moules de silice mésoporeuse et une voie solvothermale. L'insertion du manganèse a été réalisée de deux manières : soit ab initio dès le début de la synthèse, soit a posteriori par imprégnation d'un support préalablement formé avec un précurseur de manganèse. Des oxydes mixtes mésoporeux ou des oxydes de manganèse supportés sur des oxydes mésoporeux de Ti, Zr et Ce ont été réalisés. Si la texture de ces matériaux est relativement préservée, d'importantes ségrégations du manganèse ont parfois été observées après réaction. Ces catalyseurs ont été évalués dans l'OVHC de la méthylamine, une molécule organique azotée prise pour modèle. Ils sont tous actifs dans la dégradation de la méthylamine. Toutefois, ceux associant le manganèse au cérium sont les plus performants, devant les matériaux manganèse-zirconium et manganèse-titane. Deux voies de dégradation de la méthylamine ont été mises en évidence. Quel que soit le catalyseur, la première voie mène à la formation d'ions NH4 +, HCOO-, NO2 - et NO3 - présents en phase aqueuse. Les ions ammonium et formiates, formés en quantités équimolaires en tout début de réaction, sont des produits primaires de cette réaction. Les ions ammonium sont réfractaires à l'oxydation et s'accumulent dans le milieu réactionnel alors que les ions formiates sont complètement minéralisés en CO2 et H2O en fin de réaction. Nitrites et nitrates sont détectés à l'état de traces. La deuxième voie conduit directement et très majoritairement à N2 et CO2, sans qu'aucun autre composé ne soit détecté intermédiairement en phase liquide. Cette dernière voie peut représenter jusqu'à 50% de la dégradation de la méthylamine. En fin de réaction, la totalité de la fraction carbonée de la méthylamine a été minéralisée en CO2 et la sélectivité en diazote atteint jusqu'à 50% / Heterogeneous manganese based oxide associated to titanium, zirconium or cerium dioxide catalysts (Mn-Ti-O, Mn-Zr-O and Mn-Ce-O) were prepared using different synthesis route and evaluated in the Catalytic Wet Air Oxidation (CWAO) of methylamine. Various synthesis routes were investigated to prepare the catalysts, especially the sol-gel method using block copolymers, the nano-casting approach in mesoporous silicate templates and the solvothermal synthesis. Introduction of manganese was achieved in two different ways: either ab initio, from the beginning of the synthesis or a posteriori via impregnation of the support with a manganese precursor. If the textural properties of these materials are almost unchanged after reaction, an important segregation of the manganese was sometime observed. These catalysts were evaluated in the CWAO of methylamine, a model nitrogen-containing organic molecule. All catalysts were active in the degradation of methylamine. However, those combining manganese and cerium were performing much better than the manganese-zirconium and manganese-titanium ones. Two degradation pathways were evidenced. Whatever the catalyst, the first degradation route led to the formation of NH4 +, HCOO-, NO2 - and NO3 - ions in the aqueous phase. Ammonium and formate ions were produced in equimolar amount at the beginning of the reaction and appeared as primary products. Ammonium ions were refractory toward further oxidation and accumulated in the reaction mixture, while formate ions were totally mineralized to CO2 and H2O by the end of the reaction. Nitrite and nitrate ions were detected in trace amount. The second pathway would directly and mainly lead to N2 and CO2, without any intermediate compound being detected in the liquid phase. This last pathway would account for 50% of the degradation of methylamine. At the end of the reaction, the carbon fraction in methylamine was totally mineralized to CO2 and the selectivity in molecular nitrogen reached up to 50%

The 2,4-Dichlorophenol (2,4-DCP) solution (400 mg L¡Ð1) was treated by a wet air oxidation (WAO) process at temperatures of 393¡Ð453 K under a total pressure of 3.0 MPa using either Mn /£^-Al2O3 or Mn-Ce /£^-Al2O3 composite oxide as a catalyst. A COD reduction was found only 19.2% within 60 min if the WAO process was performed in a semi-batch type reactor without any catalyst addition; however, a higher COD removal of 69.4% or 71.4% was achieved when the Mn /£^-Al2O3 or Mn-Ce /£^-Al2O3 oxide was applied in the WAO process, respectively. A catalytic wet air oxidation (CWAO) of 2,4-DCP solution using the Mn-Ce /£^-Al2O3 oxide as a catalyst was conducted in another up-flowing fixed-bed reactor at 433 K under a pressure of 3.0 MPa in a space velocity of 4.0 hr¡Ð1. The COD reduction of the solution of 2,4-DCP was found above 61.4%. Also, both BOD5 and COD values in the effluent from the CWAO process was examined, and the BOD5/COD ratio was about 0.64. On the other hand, it is possible to treat the 2,4-DCP solution (¡Õ400 mg L¡Ð1) to meet the discharging regulation standard (COD¡Õ100 mg L¡Ð1) began in 1998 at Taiwan using a CWAO run and followed by an activated sludge treatment unit. The Ea values of the CWAO of 2,4-DCP using the Mn /£^-Al2O3 oxide as a catalyst were 20.77 KJ mol¡Ð1 and 23.99 KJ mol¡Ð1, respectively, for the first-stage and the second-stage reaction, respectively. In addition, the Ea values of the CWAO of 2,4-DCP over the Mn-Ce /£^-Al2O3 oxide were 14.77 KJ mol¡Ð1 and 23.30 KJ mol¡Ð1, respectively, for the first-stage and the second-stage reaction. Obviously, the Mn-Ce /£^-Al2O3 oxide does a better job in reducing the activation energy of the CWAO of 2,4-DCP than the Mn /£^-Al2O3 oxide does. Unfortunately, 2,4-DCP is hardly decomposed to become a low molecule weight carbon acids by the WAO run undergoing at 493 K without any catalyst addition. Several intermediates, such as 2-chlorophenol, phenol, catechol, oxalic acid, and formic acid, of the effluent from the CWAO of 2,4-DCP run over the Mn-Ce /£^-Al2O3 oxide were determined with a high-performance liquid chromatography.

Des catalyseurs à base d'oxyde de manganèse ont été préparés par différentes voies et évalués dans l'Oxydation en Voie Humide Catalytique de l'ammoniaque. Les catalyseurs sont actifs, sélectifs en diazote et stables dans les conditions de la réaction. Diazote et nitrite sont des produits primaires de la réaction. Une étude approfondie de l'effet des paramètres opératoires (teneur en manganèse, pression partielle en oxygène, concentration en ammoniaque, pH initial de la solution, charge de surface du catalyseur) sur les performances catalytiques a été réalisée. La sélectivité en diazote est favorisée lorsque i) la quantité de catalyseur est faible, ii) le rapport nO2/nNH4+ est proche de la stœchiométrie (˜ 0,75) et iii) le pH au point de charge nulle du catalyseur est neutre. Bien qu'un pH fortement basique (pH 13) améliore l'activité catalytique, la conversion nitrite en nitrate est inhibée et la sélectivité en diazote est dégradée. D'un point de vue cinétique, les ordres partiels par rapport à l'oxygène et à l'ammoniaque sont de 0 et 1, respectivement. L'étude de l'influence de l'état d'oxydation du manganèse (+II, +III et +IV), en présence d'oxydes de manganèse massiques commerciaux ou de catalyseurs à base d'oxyde de manganèse supporté sur cérine, montre que le site actif serait constitué d'une paire Mn(+III)/Mn(+IV). La réaction « fait son site » et les oxydes pour lesquels le manganèse est initialement présent à un faible degré d'oxydation se trouvent fortement modifiés en cours de réaction. Une synergie entre le manganèse et le cérium est également confirmé, impliquant les deux couples redox Mn(+III)/Mn(+IV) et Ce(+III)/Ce(+IV) de manière concertée / Manganese oxide-based catalysts have been synthesized through different routes and evaluated in the Catalytic Wet Air Oxidation of ammonia. Such catalysts are active, selective towards molecular nitrogen and stable under the applied reaction conditions. Molecular nitrogen and nitrite are primary products. A detailed study of the impact of the operating conditions (manganese content, oxygen partial pressure, ammonia concentration, initial pH, and charge at the catalyst surface) on the catalytic performances was carried out. The selectivity in molecular nitrogen is optimum when i) the amount of catalyst is low, ii) the ratio nO2:nNH4+ is close to stoichiometry (˜ 0.75) and ii) the pH at the point of zero charge of the catalyst is neutral. Although strongly basic conditions (pH 13) improve the catalytic activity, the conversion nitrite to nitrate is inhibited and the selectivity in molecular nitrogen is degraded. From a kinetic point of view, the reaction order with respect to oxygen and ammonia are 0 and 1, respectively. The influence of the oxidation state of manganese (+II, +III and +IV) in the presence of bulk manganese oxides or ceria-supported manganese oxides indicated that the active site would consist of a pair of Mn(+III) and Mn(+IV). The reaction makes the active site and the oxides where manganese is initially present at a low oxidation state are markedly modified upon reaction. A synergy between manganese and cerium is also confirmed, involving the two Mn(+III)/Mn(+IV) and Ce(+III)/Ce(+IV) redox couples in a concerted way

Orientadores: João Alexandre F. da Rocha Pereira, Cesar Augusto M. de Abreu / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-07-28T21:49:09Z (GMT). No. of bitstreams: 1 Sales_FernandoGazelli_D.pdf: 3615056 bytes, checksum: 37a35bf7a6015215ae5ab7c8f1aa4bb5 (MD5) Previous issue date: 2001 / Resumo: Os materiais lignocelulósicos, representando a maior reserva natural renovável da natureza, encontram-se armazenados nas plantas sob a forma de celulose, hemicelulose, lignina e extrativos, com a lignina correspondendo cerca de 30% deste total. As rotas de beneficiamento da lignina, com destaque para os processos oxidativos, visando a produção de vanilina, principalmente, utilizam na grande maioria processos bifásicos, alguns utilizando catalisadores solúveis na fase líquida, operando no entanto, com baixos rendimentos. No presente trabalho desenvolveu-se um processo de oxidação úmida catalítica (CWAO) da lignina para a produção seletiva de aldeídos aromáticos, com ênfase na vanilina, siringaldeído e p-hidroxibenzaldeído, aplicando um catalisador de paládio suportado em y-alumina. Prevendo-se a avaliação do processo catalítico foram conduzidas experiências em reator auto clave mecanicamente agitado, operando em batelada alimentada com relação à fase gasosa. Operou-se entre 373K e 413K, a uma pressão total de 20bar, representando uma pressão parcial de oxigênio entre 2bar e 10bar. A lignina com concentração de 60gIL foi solubilizada em meio alcalino de NaOH 2N. Utilizou-se um catalisador de Pd (2,85%pp.), em y-alumina, com granulometria entre 90_m e 200_m, aplicando-se concentrações de 3%pp. a 5%pp. em relação ao volume reacional. As reações de degradação da lignina e de formação de aldeídos aromáticos foram descritas por um modelo cinético quantificado por um sistema de reações complexas do tipo série-paralelo, com etapas de pseudo-primeira ordem. A presença do catalisador resultou em níveis de rendimento e seletividade em aldeídos, muito superiores quando comparados com o processo não catalítico, representando uma redução de cerca de 50% na energia de ativação para a degradação da lignina. Os níveis de conversão da lignina em aldeídos foram de 6% a 393K, 12% a 393K e 18% a 423K, para uma pressão parcial de oxigênio de 5bar e carga de catalisador de 4%pp. Com a finalidade de produzir aldeídos aromáticos em regime contínuo, um reator de leito fluidizado trifásico contínuo foi projetado e construído, em escala mini-piloto. O sistema foi avaliado hidrodinamicamente, em testes pré-operacionais, através de análise experimental utilizada aplicou a distribuição dos tempos de residência (DTR) na fase gasosa, utilizando o gás metano como traçador. A estimação dos dois parâmetros recorreu à confrontação das previsões obtidas via função de transferência do sistema, com os resultados provenientes dos experimentos dinâmicos, adotando-se como critério a minimização de uma função objetivo através de uma subrotina de busca seqüencial. Os resultados obtidos, de 2,2% a 9,3% para a retenção gasosa, e 38,0 a 54,4 para o número de Peclet da fase gasosa, estão compatíveis com os valores publicados na literatura para reatores de dimensões semelhantes operando nas mesmas condições. A produção de aldeídos aromáticos em regime contínuo, no reator de leito fluidizado trifásico, utilizou como agente oxidante o ar atmosférico a uma pressão de 4 bar. As influências dos parâmetros operacionais foram avaliadas dentro das ITonteiras práticas de operação, isto é, vazões da fase líquida de 5,OL/h e 10LIh, temperaturas de 393K e 413K. A vazão da fase gasosa foi fixada em 1000 NL/h com uma carga de catalisador de 4%pp e granulometria de 400llm - 5001lID. A lignina foi dissolvida em uma solução alcalina de hidróxido de sódio 2N a uma concentração de 30g/L. O melhor rendimento em aldeídos aromáticos foi de 12% em relação a concentração inicial de lignina, com o reator operando a 393K e vazão da fase líquida de 5L/h / Abstract: The lignocellulosic material, representing the largest natural renewable resource, occurring in the plants under the cellulose form, hemicellulose, lignin and extractive, with the lignina corresponding about 30% of this total one. The routes of lignin chemical processing, with prominence for the oxidations processes, with the objective of vanilin production, use in the great majority two-phase processes, some using soluble catalysts in the liquid phase, operating however, with low efficiency. In the present work a process of catalytic wet air oxidation (CW AO) was developed with the objective of selective production of aromatic aldehydes, with emphasis in the vanilina, siringaldeído and p-hidroxibenzaldeído, ITom lignin, applying a palladium catalyst supported in y-alumina. Intending the evaluation of the catalytic process, experiences were carried out in a mechanically stirred high pressure autoclave reactor, in semi-batch way, in relation to the gaseous phase. It was operated in temperatures ITom 373K to 413K, at a total pressure of 20bar, representing a partia! pressure of oxygen ITom 2bar to 10bar. The lignin concentration of60gIL was in an aIkaline medium ofNaOH 2N. A palladium catalyst was used (2,85%pp.), in y-alumina, with granulometry ITom 90mm to 200mm, being applied concentrations ITom 3%pp. to 5%pp. in relation to the reactional volume. The reactions of lignin degradation and aromatic aldehydes production were described by a kinetics model quantified by a system of complex reactions of the series-parallel type, with stages of pseudo-first order. The presence of the catalyst resulted in high levels of seletivities in aldehydes, further than as compared with the non-catalytic process, representing a reduction about 50% in the activation energy for the lignin degradation. The levels of conversion ofthe lignin in aldehydes were of6% at 393K, 12% at 393K and 18% at 423K, for a partial pressure of oxygen of 5bar and catalyst loading of 4%pp. With the purpose of producing aromatic aldehydes in continuous regime way, a three-phase fluidized bed reactor was designed and built, in mini-pilot scale. The system was evaluated hydrodynamically, in pre-operational tests, through applying dynamic analysis for the gaseous phase. The hydrodynamic analysis of the system was accomplished through the values of the gaseous retention (8G) and of the ofaxial Peclet number (PeG). The experimental technique applied the residence time distribution (RTD) in the gaseous phase, using the methane gas as tracer. The estimation ofthe two parameters felI back upon the conftontation ofthe prevision obtained through transfer function ofthe system, with the results uom the dynamic experiments, being adopted as approach the minimization of a objective function through a subroutine of sequencial search. The obtained results, uom 2,2% to 9,3% for the gaseous retention, and 38,0 to 54,4 for the number of Peclet of the gaseous phase, are compatible with the values published in the literature for reactors operating in the same conditions. The aromatic aldehydes production in a continuous three-phase fluidized bed reactor, used as oxidizing agent the atmospheric air in apressure of 4 bar. The influences of the operational parameters were evaluated in the practical ranges of operation, that is, liquid phase flow rate of 5,OL/h and lOL_ temperatures of 393K and 413K. The gaseous phase flow rate was 1000 NL/h with a catalyst loading of 3%pp and granulometry of 400 j.1m 500j.1m The lignin was in an aIkaline medium of NaOH 2N, in a concentration of 30g/L. The best yield in aromatic aldehydes reached 12% in relation to lignin initial concentration, as the reactor was operating at 393K and liquid flow rate of5LIh / Doutorado / Sistemas de Processos Quimicos e Informatica / Doutor em Engenharia Química

Parmi les différents procédés chimiques, l'Oxydation en Voie Humide Catalysée (OVHC) apparaît comme une technique de choix pour le traitement des eaux usées à forte teneur en composés toxiques et peu biodégradables. Ce procédé, sous pression, est limité par la faible solubilité de l'oxygène. L'étape cruciale de la réaction est alors le transfert de l'oxygène jusqu'à la particule métallique via le support. Les phénomènes régissant ce transfert sont la composition des supports oxydes et l'interaction métal/support. L'objectif de ce travail est d'étudier l'influence de la teneur en CeO2, connue pour ses propriétés de transfert et de stockage d'oxygène, sur les propriétés de catalyseurs Ru/TiO2-x%CeO2 et Pt/TiO2-x%CeO2 en oxydation voie humide catalysée du phénol et de l'acide acétique.L'addition de cérine améliore les propriétés de stockage de l'oxygène des matériaux mais favorise (i) pour l'OVHC du phénol, la formation de polymères insolubles en solution et le dépôt d'espèces carbonées sur la surface catalytique, (ii) pour l'OVHC de l'acide acétique une carbonatation des supports. Il en résulte, dans les deux cas, une perte d'activité par blocage des sites catalytiques. Le platine s'avère plus actif que le ruthénium pour l'OVHC du phénol alors que l'inverse est observé dans le cas de l'acide acétique. / Among the different chemical processes, catalytic wet air oxidation (CWAO) appears to be a promising process for the treatment of wastewater containing high levels of toxic and poorly biodegradable compounds. This over pressure process is limited by the low oxygen solubility. The limiting step of reaction is the oxygen transfer to the metal particle through the support. Phenomena governing this transfer are the oxide support composition and the metal/support interaction. The objective of this work is to study the influence of the CeO2 content, known for its oxygen transfer and storage capacity, over the catalytic properties of Ru/TiO2-x%CeO2 and Pt/TiO2-x%CeO2 for catalytic wet air oxidation of phenol and acetic acid. The addition of ceria improves the oxygen storage capacity of materials but it enhances i) for CWAO of phenol, the formation of insoluble polymers in solution and the deposition of carbonaceous species on the catalytic surface, ii) for CWAO of acetic acid, the formation of carbonates on the support. In both cases an activity lost is due to the blocking of catalytic sites. Platinum is more active than ruthenium for CWAO of phenol while the opposite is observed in the case of acetic acid.

Abstract The large amounts of industrial wastewaters, contaminated by hazardous and toxic compounds together with ever tightening legislation, have challenged traditional wastewater treatment methods. Therefore, the development of discharge limits under, cost-effective and ecological wastewater treatment has become an essential concern. Catalytic water phase technologies are interesting alternatives for traditional wastewater treatment. Among them catalytic wet air oxidation (CWAO) has been used successfully in the management of various industrial effluents. However, the development of an active and stable catalyst for the severe reaction conditions of CWAO has proved truly challenging. The aim of this thesis was to study the activity and stability of laboratory prepared cerium supported metal catalysts in the catalytic wet air and wet peroxide oxidation of aqueous organic pollutants. Ru supported on Ce-Zr mixed oxides and commercial activated carbon as reference were used in CWAO and catalytic wet peroxide oxidation (CWPO) of surface plating industry wastewater. Ag/Ce-Zr and Pt/Ce-Ti catalysts were catalyzed CWAO of aqueous solution of bisphenol A (BPA). Both CWAO and CWPO improved the abatement of organic compounds from surface plating industry wastewater when comparing the non-catalytic experiments. Moreover, catalytic oxidation enhanced the biodegradability of organic matter in the wastewaters. According to the results, Pt/Ce-Ti catalysts performed with higher activity in CWAO of BPA than Ag/Ce-Zr catalysts and almost 100% removal of BPA was achieved. The leaching of active metal during oxidation experiments affected the activity of Ag/Ce-Zr catalysts. Moreover, CWAO of BPA was not a surface area specific reaction but the activity of catalysts was related to the chemisorbed oxygen content on the catalysts’ surface. The results of this thesis showed that cerium supported metal catalysts are active and stable catalysts in CWAO of BPA and also in the treatment of industrial wastewater. Therefore, these catalysts could be applied next to pilot scale applications. / Tiivistelmä Teollisuuden jätevedet sisältävät usein haitallisia ja myrkyllisiä yhdisteitä, joiden käsittely perinteisillä jäteveden käsittelymenetelmillä on hyvin haastavaa. Lisäksi alati kiristyvä ympäristölainsäädäntö asettaa omat vaatimuksensa jäteveden käsittelylle. Katalyyttiset vedenkäsittelymenetelmät ovat viime vuosina herättäneet paljon kiinnostusta. Yksi lupaavimmista tekniikoista on katalyyttinen märkähapetus, jota on käytetty sekä lukuisten malliaineiden että teollisten jätevesien käsittelyssä. Märkähapetuksen vaativissa reaktio-olosuhteissa aktiivisena säilyvän katalyyttimateriaalin kehittäminen on kuitenkin osoittautunut varsin haasteelliseksi. Väitöskirjatutkimuksen tavoitteena oli kehittää aktiivisia ja kestäviä ceriumpohjaisia katalyyttimateriaaleja märkähapetusreaktioon. Tutkimuksessa valmistettiin Ru-, Pt- ja Ag-katalyyttejä, jotka impregnoitiin Ce-Zr- ja Ce-Ti-sekaoksideille. Ru/Ce-Zr-katalyyttejä sekä kaupallista aktiivihiiltä vertailumateriaalina käytettiin pintakäsittelyteollisuuden jäteveden märkähapetuksessa ja märkäperoksidihapetuksessa. Bisfenoli A:n (BPA) vesiliuoksen märkähapetusta katalysoitiin sekä Ag/Ce-Zr- että Pt/Ce-Ti-katalyyteillä. Katalyyttisellä märkähapetuksella ja märkäperoksidihapetuksella pintakäsittelyteollisuuden jäteveden orgaanisten yhdisteiden konsentraatio väheni enemmän verrattuna ilman katalyyttiä suoritettuihin hapetuksiin. Lisäksi käsitellyn vesinäytteen biohajoavuusaste nousi eli jäteveden sisältämät orgaaniset yhdisteet olivat hapettuneet helpommin biohajoavaan muotoon. Pt/Ce-Ti-katalyytit olivat Ag/Ce-Zr-katalyyttejä aktiivisempia BPA:n märkähapetusreaktiossa. Pt-katalyyttisessä reaktiossa saavutettiin lähes 100 % reduktio BPA:n pitoisuudessa. Ag-katalyyttien aktiivisuuteen vaikutti hopean osittainen liukeneminen hapetettavaan liuokseen märkähapetusreaktion aikana. Lisäksi havaittiin, että BPA:n märkähapetusreaktiossa katalyytin aktiivisuus oli riippuvainen katalyyttipintaan kemiallisesti sitoutuneen hapen määrästä eikä niinkään katalyytin pinta-alasta. Väitöskirjatutkimuksessa saatujen tulosten perusteella valmistetut ceriumpohjaiset metallikatalyytit olivat aktiivisia ja kestäviä. Katalysoiduissa hapetusreaktiossa sekä BPA:n että pintakäsittelyteollisuuden jäteveden orgaaninen kuormitus pieneni. Siksi valmistettuja katalyyttimateriaaleja voitaisiin tutkia seuraavaksi pilotti-mittakaavan sovellutuksissa.

Des catalyseurs à base de métaux nobles (Pt, Pd, Ir, Ru et Rh) supportés (TiO2, ZrO2, CeO2 et CeZrO2) ont dans un premier temps été préparés. L'Oxydation en Voie Humide Catalytique de l'ammoniaque en présence de ces catalyseurs a alors été réalisée. Le platine est le métal le plus actif. L'iridium et le palladium sont les plus sélectifs en diazote. Le catalyseur Pt/TiO2 est le plus performant car il combine une très forte activité et une sélectivité en diazote peu éloignée de celles de l'iridium et du palladium. Une étude approfondie sur ce catalyseur (méthode de préparation, nature du précurseur métallique,…) a montré que seule la basicité de surface du catalyseur a un impact négatif sur la sélectivité en diazote. Les autres paramètres étudiés sont non significatifs. Le travail réalisé sur les conditions opératoires (PO2, T, mcatalyseur, pH et concentration d'ammoniaque) toujours en présence de Pt/TiO2 ont montré qu'il est nécessaire de contrôler la fonction oxydante et notamment le rapport nO2/nNH3. En effet, si la valeur de ce rapport est trop élevée (nO2/nNH3 >> 0,75) alors la sélectivité en diazote se dégrade fortement. Pour terminer, des catalyseurs bimétalliques PtIr/TiO2 et PtPd/TiO2 ont été préparés afin d'allier l'activité du platine à la sélectivité en diazote du palladium ou iridium. L'utilisation de ces catalyseurs s'avère peu intéressante car leur comportement est similaire à celui des mélanges mécaniques. De plus, la sélectivité en diazote est également dégradée pour nO2/nNH3 >> 0,75 avec ces catalyseurs / TiO2, ZrO2, CeO2 and CeZrO2 supported noble metal catalysts (Pt, Pd, Ir, Ru and Rh) have been in a first time prepared to be used in the Catalytic Wet Air Oxidation of ammonia. The first results show that platinum is the most active metal. Palladium and iridium are the most selective toward nitrogen. Pt/TiO2 is the most interesting catalyst because it combines a very strong activity and a selectivity toward nitrogen close to iridium and palladium. An in-depth study on this catalyst (preparation method, nature of the metallic precursor…) shows that the single parameter which has a negative impact on the selectivity toward nitrogen is the basicity of the catalyst surface. The work realized on the operating conditions (PO2, catalyst weight, pH and ammonia concentration) in the presence of Pt/TiO2 shows the necessity to control the oxidizing function and particularly the nO2/nNH3 ratio. Indeed, if the value of this ratio is too high (nO2/nNH3 >> 0,75) then the selectivity toward nitrogen degrades strongly. To end, PtIr/TiO2 and PtPd/TiO2 bimetallic catalysts have been prepared to combine the activity of the platinum and the selectivity of palladium/iridium to nitrogen. These catalysts are not interesting because their behaviour is similar to the mechanical mixtures. Furthermore, the selectivity toward nitrogen is also degraded for nO2/nNH3 >> 0,75 with these catalysts