Potreba za uklanjanjem organskih nečistoća iz industrijskih otpadnih voda uvjetovala je razvoj novih, djelotvornih tehnologija s posebnim naglaskom na uštedu sirovina i energije te ekonomičnost ...procesa. Katalitička oksidacija organskih zagađenja vodikovim peroksidom u vodenom mediju, poznata kao metoda CWPO (eng. Catalytic Wet Peroxide Oxidation), jedan je od postupaka koji ispunjava navedene zahtjeve. Upotrebom vodikova peroksida, kao oksidacijskog sredstva, i pogodnog heterogenog katalizatora moguće je proces provoditi pri atmosferskom tlaku i temperaturi ispod 383 K. Zeoliti su zbog svojih specifičnih značajki (selektivnost prema veličini i obliku molekula, termička i kemijska stabilnost, neškodljivost živom svijetu) izrazito pogodni katalizatori za uporabu u selektivnim oksidacijskim procesima. Stoga su u ovom radu proučavani aktivnost, selektivnost i stabilnost katalizatora Cu/Y-5 u reakciji oksidacije fenola vodikovim peroksidom. Katalizator je pripravljen ionskom izmjenom protoniranog oblika komercijalnog zeolita. Karakterizacija katalizatora obuhvaćala je rendgensku difrakciju (XRD), pretražnu elektronsku mikroskopiju (SEM) i elementnu analizu atomskim apsorpcijskim spektrometrom (AAS), te određivanje specifične površine i obujma pora (standardna BET-metoda). Reakcija je provođena u šaržnom Parrovu reaktoru pri atmosferskom tlaku i temperaturama od 323 do 353 K. Katalizator je pripravljen u praškastom obliku, a maseni udjel bakra u zeolitu iznosio je 3,46 %. Početna koncentracija fenola u reakcijskoj otopini bila je 0,01 mol dm−3, a vodikova peroksida od 0,01 do 0,10 mol dm−3. Dobiveni eksperimentalni podaci testirani su sljedećim kinetičkim modelima za oksidaciju fenola rPh = k1 cPh cHP i raspad vodikova peroksida rHP = k2 cHP, a kinetički parametri procijenjeni su Nelder-Meadovom metodom nelinearnog optimiranja. Rezultati provedenih istraživanja pokazali su da je pri ispitivanim reakcijskim uvjetima primjenom postupka CWPO uz katalizator Cu/Y-5 moguće iz početne reakcijske smjese u potpunosti ukloniti fenol uz istodobno 54,5 %-tno smanjenje sadržaja ukupnog organskog ugljika.
Olive oil mill wastewater (OOMW) – the liquid waste generated in the process of olive oil extraction contains significant amounts of phenolics. Their high polluting charges that are measured in BOD5 ...and COD levels up to 35 g dm-3 and the presence in the concentrations up to 10 g dm-3 are of special concern to the environment. These compounds make OOMW biorefractory in nature and unsusceptible to a conventional biological treatment. Reducing their toxicity prior to the conventional treatment is therefore of the uttermost importance. The non-selective catalytic wet peroxide oxidation (CWPO) process is one of the methods that can be used for that purpose in practice. With the use of catalysis the process can be successfully operated under mild conditions with low energy consumption. In this work, the influence of the reaction parameters and the catalyst preparation method on the activity and stability of zeolite (13X) based catalyst in the reaction of hydrogen peroxide oxidation of phenolic compounds present in wastewater from industry for processing olives and olive oil was examined. The reaction was carried out in a batch reactor at different stirring speed, particle sizes, temperatures, catalyst loadings and initial concentrations of hydrogen peroxide. The catalyst Cu/13X was prepared by ion exchange of commercial 13X zeolite. Characterization of the catalyst included N2 physisorption, XRD, TPD-CO2 and FTIR-Pyridine desorption. In order to increase the catalyst’s stability, it was subjected to a thermal post-synthesis treatment at 1273 K. The justification for post synthesis treatment of the catalyst is reflected in the enhanced stability of the catalytically active material which is removed from the carrier, i.e. larger resistance of Cu/13X - K1273 to leaching. Examining the effect of the mixing rates and catalyst particle sizes on reaction rate it was found that the reaction is carried out in the kinetic regime, with the total phenols content diminished by more than 80 % with a 20 % decrease in wastewater’s TOC content and leaching below 3 wt. %.
Phenol oxidation with hydrogen peroxide using Cu/ZSM5 and Cu/Y5 catalysts In this work, catalytic activity and stability of Cu/Y5 and Cu/ZSM5 zeolites in phenol oxidation with hydrogen peroxide were ...examined. The catalyst samples were prepared by the ion exchange method of the protonic form of commercial zeolites. The catalysts were characterized by the powder X-ray diffraction (XRD), AAS, while the adsorption techniques were used to measure the specific surface area. The thermal programmed desorption of NH3 (NH3-TPD) was used for measuring the total number of acid sites formed on the surface of zeolites. Catalytic performance of the prepared samples was monitored in terms of phenol, hydrogen peroxide and total organic carbon (TOC) conversion, by-product distribution and a degree of copper leached into the aqueous solution. It was found that the activity of Cu/Y5 catalyst was generally higher than that of Cu/ZSM5 and that unlike Cu/ZSM5, Cu/Y5 catalyzed phenol oxidation more completely.
Copper bearing 13X zeolite was prepared from commercial 13X zeolite via ion-exchange with copper acetate solutions. After the incorporation of copper, Cu/13X catalyst was exposed to post synthesis ...thermal treatment at different temperatures. The prepared catalysts were characterized by XRD and FTIR, while the adsorption techniques were used for the measurement of the specific surface area and pore volume. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at atmospheric pressure in temperature range from 333 to 353 K. Influence of postsynthesis thermal treatment and reaction temperature on activity and stability of prepared catalysts in the catalytic wet oxidation process with hydrogen peroxide as oxidant was investigated. The experimental results showed that total degradation of phenol can be achieved under mild operating conditions at temperatures bellow 353 K. All catalysts exhibited higher activity in terms of hydrogen peroxide and phenol abatement with the increasing temperature of the reaction. The postsynthesis thermal treatment resulted in more stable catalyst with respect to stability of both catalysts’ active metal component (copper) and support, while the activity of catalysts in terms of TOC conversion remained unaltered.
This work reports the results of experimental and theoretical investigation of toluene oxidation on different metal oxide based catalysts (manganese oxide, MnOx, mixed manganese-iron oxide, MnFe, ...perovskite-type manganese oxide, LaMnO3 and commercial Pt-Al2O3 catalyst). Particular attention was devoted to single and mixed manganese based oxides and ceria based materials as alternatives to conventionally used noble metal containing catalysts. Toluene oxidation was performed under steady-state conditions in an integral fixed bed reactor operating over a wider range of reaction temperatures and at various space times. The influence of reaction variables on the rate of toluene oxidation was examined using the simple first-order kinetic model and the one-dimensional (1D) pseudo-homogeneous model to describe the reaction system. The proposed model was verified comparing the theoretical predictions with the experimental laboratory results. The results of catalytic tests indicated that the mixed manganese-iron oxide (MnFe) exhibited remarkable catalytic activity for the toluene oxidation, almost comparable with the activity of the commercial Pt-Al2O3. The reaction temperature T50 corresponding to 50% of the toluene conversion was observed at 419 K for the MnFe oxide and at 405 K for the Pt-Al2O3. A very good agreement of experimental data with the proposed 1D model was obtained. Based on the shape of the light-off curve and the values of the apparent activation energies, which decreased from 120.36 kJ/mol to 16.88 kJ/mol with reaction temperature increase, it was concluded that the reaction rate was probably limited by the mass transfer, no matter the relatively small catalyst particle size fraction employed in this study (315 - 400µm).
Katalitička oksidacija zagađivala organskog podrijetla vodikovim peroksidom u vodenom mediju, poznata kao metoda CWPO (eng. Catalytic Wet Peroxide Oxidation), jedan je od postupaka kojim je moguće ...postići smanjenje organskog opterećenja otpadnih voda u praksi. U ovom radu zeolit Y-5 izabran je za nosač u koji je kao katalitički aktivna tvar ugrađen bakar. U radu je istražen utjecaj reakcijskih parametara te postsintetske kemijske i termičke obrade katalizatora na njegove katalitičke značajke: aktivnost i stabilnost. Katalizator Cu/Y-5 pripravljen je ionskom izmjenom protoniranog oblika komercijalnog zeolita Y-5. Radi poboljšanja njegovih katalitičkih značajki provođena je postsintetska kemijska (ispiranje sa H2SO4) i termička obrada (kalciniranje). Karakterizacija katalizatora Cu/Y-5 obuhvaćala je rengdensku difrakcijsku analizu na praškastom uzorku (PXRD) i elementnu analizu na atomskom apsorpcijskom spektrometru (AAS) te određivanje specifične površine, obujma pora i raspodjele obujma pora (standardna metoda BET). Aktivnost i stabilnost pripravljenih katalizatora ispitana je u reakciji oksidacije fenola vodikovim peroksidom u vodenoj otopini. Maseni udjel bakra na zeolitu bio je 3,46 % prije postsintetske obrade, odnosno 3,97 % nakon postsintetske termičke obrade te 0,94 % nakon postsintetske kemijske obrade. Eksperimentalni podatci dobiveni provođenjem katalitičkih testova testirani su sljedećim kinetičkim modelima za oksidaciju fenola rPh = k1 cPh cHP i raspad vodikova peroksida rHP = k2 cHP. Za procjenu kinetičkih parametara primijenjena je Nelder-Meadova metoda nelinearnog optimiranja. Oba postupka postsintetske obrade značajno su poboljšala stabilnost pripravljenog Cu/Y-5 katalizatora, dok je istodobno njegova aktivnost ostala nepromijenjena ili je poboljšana.
In this study the physico-chemical and catalytic properties of copper bearing MFI zeolites (Cu-MFI) with different Si/Al and Si/Cu ratios were investigated. Two different methods for incorporation of ...metal ions into the zeolite framework were used: the ion exchange from the solution of copper acetate and the direct hydrothermal synthesis. Direct synthesis of a zeolite in the presence of copper-phosphate complexes was expected to generate more active copper species necessary for the desired reaction than the conventional ion exchange method. Direct decomposition of NO was used as a model reaction, because this reaction still offers a very attractive approach to NO
removal. The catalytic properties of zeolite samples were studied using techniques, such as XRD, SEM, EPR and nitrogen adsorption/desorption measurements at 77 K. Results of the kinetic investigation revealed that both methods are applicable for the preparation of the catalysts with active sites capable of catalyzing the NO decomposition. It was found out that Cu-MFI zeolites obtained through direct synthesis are promising catalysts for NO decomposition, especially at lower reaction temperatures. The efficiency of the catalysts prepared by both methods is compared and discussed.
The heterogeneous catalytic wet peroxide oxidation (CWPO), involving total oxidation of organic compounds to CO2 and H2O is a possible path for the treatment of toxic and bio‐refractory wastewater ...streams. The aim of this work was to synthesize and characterize three Cu/ZSM5 catalysts prepared by direct hydrothermal synthesis. The mass ratio of the active metal component in the zeolite ranged from 1.62–3.24 wt %. These materials were tested for CWPO of aqueous phenol in a stainless steel Parr reactor, in batch operation under mild conditions (at atmospheric pressure and a temperature of 353 K). The catalyst weight was 0.1 g dm–3 and the initial concentration of phenol and hydrogen peroxide were 0.01 mol dm–3 and 0.1 mol dm–3, respectively. The catalysts were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), AAS and ICP‐MS. Their catalytic performance was monitored in terms of phenol and total organic carbon (TOC) conversion, hydrogen peroxide decomposition, by‐product distribution and the degree of copper leached into the aqueous solution. The experimental results indicated that within 180 min, these catalysts facilitated almost complete elimination of phenol and a significant removal of chemical oxygen demand, without significant leaching of Cu ions from the zeolite. The Cu/ZSM5‐DHS3 catalyst with the highest copper loading was proven to be the best candidate. The useful fraction of hydrogen peroxide that contributed to the removal of the organic compounds quantified in terms of selectivity, S, indicated that the CWPO selectivity was always less than 100 %, which meant that there was some self‐degradation of oxidant. It was also shown that oxidation of phenol took place on the catalyst surface via a heterogeneous mechanism, and that the contribution of any homogeneous reaction mechanism was not significant.
Cu/ZSM5 zeolites with varying Si/Cu ratios are prepared by direct hydrothermal synthesis and tested for phenol oxidation with hydrogen peroxide at atmospheric pressure and 353 K. The best suitable catalyst shows the highest copper load. It is demonstrated that the oxidation of phenol takes place on the catalyst surface via a heterogeneous mechanism.
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