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.

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology / Fenton oxidation is classified into two processes, homogeneous and heterogeneous. Homogeneous Fenton oxidation process, have been shown to be efficient in the degradation of organic pollutants. However, it was shown to have limitations which can be addressed by the heterogeneous Fenton oxidation. Despite the high efficiency of the heterogeneous Fenton oxidation process in the degradation of recalcitrant organic pollutants, the currents synthesis trends of the heterogeneous Fenton catalyst have been proven to be time and energy constraining, since it involves the multi-step were the activated carbon have to be prepared first then co-precipitate the iron oxide on the activated carbon. However, as much as the heterogeneous Fenton catalyst has been proven to have high catalytic activity towards degradation of organic pollutants, these catalysts have some limitations, such limitations include metal ions being leached from the catalyst support into the treated water causing catalyst deactivation and a secondary pollution to the treated water. In this thesis, these catalysts have been applied in the degradation of recalcitrant organic pollutants such as methylene blue and phenols. This study focuses on the single step synthesis of iron oxide nanoparticles supported on activated carbon, were carbonaceous material is impregnated with iron salt then pyrolysed via microwave heating. Microwave power and the amount of iron salt were optimized. The prepared activated carbon-iron oxide composites were applied to the degradation of 2-nitrophenol (2-NP) and methylene blue (MB). Methylene blue was used as a model compound due to the fact that it is easier to monitor the degradation process with UV-Vis as compared to 2-nitrophenol . 2-nitrophenol the additional step for the adjustment of pH is required since nitrophenols are colorless in color at lower pH. The characterization showed that the microwave power and the amount of the iron precursor have an influence on the porosity and surface functional groups of the activated carbon. Further it was vi observed that microwave power and iron precursor influnces the amount of iron oxide formed on the surface of the support. It was also observed that the activated carbon-iron oxide composite have the catalytic effects on the Fenton oxidation process of MB and 2-NP. The parameters such as H2O2, pH, catalyst dose, initial concentration, temperature affect the degradation of both MB and 2-NP. Kinetics studies showed that Fenton is a surface driven reaction since the results fitted the pseudo first order model. The thermodynamics parameters also showed that the reaction is endothermic, spontaneous and is randomized. This implies that the reaction of the degradation of MB and 2-NP is feasible and the catalysts prepared have high catalytic activity. MB and 2-NP were degraded to smaller organic molecules (carboxylic acids). The stability of the catalyst observed to decrease as the number of cycles increased, this is due to the leaching of iron ions from the support material. Hence it was concluded that the activated carbon-iron oxide composite was successfully synthesized and had the high catalytic activity for the degradation of MB and 2-NP.