Dissertationen zum Thema „Oxidační procesy“

In the master’s thesis are expleined and described proceses and terms related by problematic degradation of pesticides using advenced oxidation proceses and their possibilities of determinations. The essence of the experimental work was development and validate created method for determination of chosen pesticides. Degradation of this pesticides by advenced oxidation proceses and their determination after degradation. The aim of the work was compare chosen oxidation methods and summary of results for designe of the most appropriate method.

This thesis deals with advanced oxidation processes (AOPs) and it’s use for removal of micropollutants from wastewater. The first chapter explains the need AOPs, water quality, pollution and substances that are present in the water. Further, the first chapter outlines approach of the current legislation to micropollutants. The second chapter explains the theory and principle of operation of AOPs. This chapter is divided into two sections. The first section describes AOPs, which were tested at selected WWTP. In the second section, there are described some other AOPs. The third chapter is a literature retrieval of AOPs dealing with the removal of micropollutants. This chapter is focused on the removal of hormones by AOPs using ozone-based AOPs. The fourth chapter describes the actual testing of selected AOPs. The chapter describes selected WWTP, pilot-scale AOP unit and test results. In the last chapter there is designed and described full-scale AOP tertiary unit for removing of micropollutants. The last chapter also contains economic analysis of the proposed tertiary unit.

Recently, an increasing problem in wastewater treatment is the insufficient removal of organic pollutants. These substances can be toxic to the environment already in a small amount, either acutely or chronically. The goal is therefore to develop of technologies that ensure their effective removal. One possibility is to use advanced oxidation processes. Advanced oxidation processes work on the principle of non-selective oxidation mediated by OH radicals. Several methods such as O3/H2O2 (Peroxone), UV/H2O2 or Fenton´s reaction can be used to generate them. The aim of this thesis was to evaluate the effectiveness of the used advanced oxidation processes in wastewater treatment via ekotoxicity tests. Wastewater samples treated with advanced oxidation processes on the pilot unit showed low values of acute toxicity for selected test organisms (D. magna, T. platyurus, S. alba, L. minor). For the sample of waste water that was treated with the UV/H2O2 on AOP laboratory unit, there was an increase in acute toxicity on the testing organism D. magna and L. minor. The similar effect was observer in the tests with the D. magna with the model samples treated with the same method, while the tests on the L. minor showed a reduction in toxicity.

This diploma thesis deals with the efficiency of removal of pharmaceuticals from drinking water by selected adsorption materials. The first part describes sources of pharmaceuticals in drinking water and possible ways of contaminating water by pharmaceuticals. Subsequently, the pharmaceuticals most commonly found in the environment - nonsteroidal anti-inflammatory drugs, antibiotics, psychiatric drugs and sex hormones - are described in more detail. Next, the thesis describes the processes used for removal of pharmaceuticals. These are activated carbon adsorption, membrane processes and advanced oxidation processes. The last chapter of the theoretical part of the thesis deals with water treatment plants, where the technologies for removing drugs are already in operation. In the practical part of this thesis an experiment was performed and evaluated, for a purpose of comparing the efficiency of selected sorption materials in the removal of diclofenac from water. Filtrasorb F100, Bayoxide E33 and GEH were used.

The aim of this diploma thesis is the determination of selected organic pollutants with a focus on artificial sweeteners in waste water from wastewater treatment plant (WWTP) Modřice and the subsequent degradation of the thus obtained concentrations in model water using advanced oxidation processes (AOP). Two sweeteners were determined, namely sucralose and saccharin found in waste water. Synthetic sweeteners are not sufficiently cleaned in the WWTP and penetrate the environment. Effective processes for removing organic substances, including alternative sweeteners, are AOP processes. These processes are based on reactions of highly reactive hydroxyl radical (OH·), which is produced by many chemical reactions. Generally, they use ozone (O3) and hydrogen peroxide (H2O2). On sampling, wastewater samples were treated with Solid Phase Extraction (SPE) and then evaluated by HPLC/MS (High Performance Liquid Chromatography). In observing the degradation of selected sweeteners, three AOP methods were used: O3/UV, H2O2/UV and O3/H2O2. For each of these methods, the efficiency of degradation of sucralose and saccharin was investigated. From the evaluated data it was found that the most efficient AOP process for removing artificial sweeteners from water is the O3/H2O2 method.

This diploma thesis focuses on possibilities of applications of UV radiation to remove pollutants from water. It summarizes sources of UV radiation and list their benefits and properties. The thesis characterizes so called advanced oxidation processes using UV light. Degradation pathways od pyridine and its derivatives especially halogenated pyridines are described. The photodegradability of pyridine and a rate of this reaction in model water is investigated in the experimental part. Also, the effect of concentration and dose of H2O2 is assessed. Gas chromatography was used to determinate concentrations of pyridine in samples.

Rešerše se zabývá teorií technologického způsobu zpracování materiálů, tzv. povrchového tavení. V první části rešerše je popsána samotná technologie a základní parametry ovlivňující proces tavení. Ve druhé části je uvedeno srování dvou základních typů laserů, a to Nd:YAG a CO2 laser. CO2 laser byl použit v případě našeho experimentu. Třetí část se zabývá vlastnostmi TiAl intermetalických slitin, především jejich fázemi -TiAl a -Ti3Al. Na závěr teoretické části je zmíněna oxidace TiAl intermetalických slitin. Experimentální část je věnována přetavování povrchu slitiny Ti-46Al-0,7Cr-0,1Si-7Nb-0,2Ni, a to v ochranné atmosféře dusíku. Tato část obsahuje výsledky několika experimentů, na jejichž základě bylo nutné stanovit potřebné parametry pro požadovaný proces tavení. Posledním krokem experimentu byla snaha o zvýšení hmotnosti vzorků v důsledku následné oxidace.

At present, the issue of occurrence of female sex hormones, estrogens and progestogens, in aquatic ecosystems is often discussed by experts and the general public. These substances of steroid structure can be difficult to remove completely by conventional wastewater and drinking water treatment technologies. In given context advanced oxidation processes based on in situ generation of highly reactive hydroxyl radicals can be a suitable technique. This thesis deals with the study of kinetics and degradation products of photocatalytic decomposition of seven female sex hormones (estrone, -estradiol, estriol, ethinylestradiol, diethylstilbestrol, progesterone and norethindrone). Experiments were conducted in a laboratory glass reactor, which was equipped with an energy efficient UV-A LED light source (365 nm emission wavelength) and an immobilised photocatalyst in a form of TiO2 five-layer film deposited on glass. Model samples of water with the initial hormone concentration of 1 mg·L-1 were used and the degradation process was monitored by an HPLC-MS method. In the given system all compounds of interest except estriol had very significant tendency to be adsorb. In the case of estriol the formal rate constant of photocatalytic decomposition was determined based on the Langmuir-Hinshelwood model for two different initial concentrations, 0.5527 hour-1 (1 mg·L-1) and 0.1929 hour-1 (5 mg·L-1), and by comparison of these values it was found that the higher degraded compound concentration, the slower decomposition (fivefold increase of the initial concentration resulted in the constant decrease to almost one-third). Moreover nine degradation products of estriol photocatalytic decomposition were recorded and their structure was designed based on mass spectra. In the second thematic part of the thesis attention was paid to development of a SPE-HPLC-MS method for simultaneous determination of female sex hormones in water ecosystems, with emphasis on an extraction part optimization. The final samples treatment process included besides extraction with Supel™ Select HLB 200 mg SPE cartridges also mechanical impurities removal, hormones extraction from solids trapped on filtration material, sample acidification and extract purification with Supelclean™ ENVI-Florisil® cartridges. Optimised method was used for determination of female sex hormones in two Brno rivers, Svitava and Svratka. In the most cases the concentration was below the detection or quantification limit.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2006.
This work focuses on the effects of hydrogen peroxide concentration on the catalytic activity and product selectivity in the liquid-phase hydroxylation of phenol over titanium-substituted zeolites Al-free Ti-Beta and TS-1 in water and methanol solvents. Hydroquinone is typically the desired product, and these solvents employed have previously been shown to be of importance in controlling the selectivity of this reaction. Different volumetric quantities of an aqueous 30 wt-% peroxide solution were added to either water or methanol solutions containing the catalyst and phenol substrate, and the reaction monitored by withdrawing samples over a period of 6-8 hours. For Al-free Ti-Beta catalysed reactions, the peroxide concentration affects the selectivity and activity differently in water and methanol solvents. Using methanol solvent, the selectivity to hydroquinone formation is dominant for all peroxide concentrations (p/o-ratio > 1), and favoured by higher initial peroxide concentrations (> 1.27 vol-%), where p/o-ratios of up to can be reached; in water solvent, increasing the peroxide concentration above this level results in almost unchanging selectivity (p/o-ratio of ca. 0.35). For lower peroxide concentrations in water, the p/o-ratio increases slightly, but never exceeds the statistical distribution of ca. 0.5. Using water as a solvent, higher phenol conversion is obtained as the initial peroxide concentration increases; in methanol the phenol conversion is largely independent of peroxide concentration. As expected for the smaller pore TS-1, higher hydroquinone selectivity is obtained in methanol than for Al-free Ti-Beta, which is consistent with shape-selectivity effects enhanced by the use of this protic solvent. Interestingly, with TS-1 the p/o-ratio is higher at lower phenol conversions, and specifically when the initial peroxide concentration is low (p/o-ratio exceeding 3 were obtained at low phenol conversion), and decreases to a near constant value at higher conversions regardless of the starting peroxide concentration. Thus, low peroxide concentrations favour hydroquinone formation when TS-1 is used as the catalyst. Comparing the performance of the two catalysts using methanol solvent, the phenol conversion on TS-1 is more significantly influenced by higher hydrogen peroxide concentrations than Al-free Ti-Beta. However, with higher initial concentrations the unselective phenol conversion to tars is more severe since the hydroquinone selectivity is not higher at these high peroxide concentrations. The increased tar formation, expressed as tar deposition on the catalyst or as the tar formation rate constant, confirms that the greater amount of free-peroxide present is mainly responsible for the non-selective conversion of phenol. Kinetic modelling of the reaction data with an overall second-order kinetic model gave a good fit in both solvents, and the phenol rate constant is independent of changing hydrogen peroxide concentration for the hydroxylation over Al-free Ti-Beta using water as the solvent (kPhenol = 1.93 x 10-9 dm3/mmol.m2.s). This constant value suggests that the model developed to represent the experimental data is accurate. For TS-1 in methanol solvent the rate constant is also independent of peroxide concentration (kPhenol = 1.36 x 10-8 dm3/mmol.m2.s). The effect of the method of peroxide addition was also investigated by adding discrete amounts over a period of 4.5 hours, and was seen to improve hydroquinone selectivity for reaction on both catalysts, and most significantly for Al-free Ti-Beta in methanol solvent. With TS-1, the mode of peroxide addition had little influence on phenol conversion, but the initial selectivity to hydroquinone was ca. 1.6 times higher than for an equivalent single-portion addition (at a similar phenol conversion). Discrete peroxide addition for hydroxylation in methanol over Al-free Ti-Beta gave greatly improved hydroquinone selectivities compared to the equivalent single-dose addition. Compared to TS-1, the initial selectivity was not as high (p/o-ratios of 0.86 and 1.40 respectively at 10 mol-% phenol conversion), but this can be explained on the basis of geometric limitations in the micropores of TS-1 favouring hydroquinone formation. The final selectivity, however, is marginally higher (using the same mode of peroxide addition, and at the same phenol conversion). Discrete peroxide addition has an additional benefit in that it also reduces the quantity of free-peroxide available for product over-oxidation, and consequently reduces the amount of tars formed. Thus, the interaction of the effects of peroxide concentration and the solvent composition and polarity on the product selectivity and degree of tar formation is important. Particularly with TS-1, lower peroxide concentrations in bulk methanol solvent are highly beneficial for hydroquinone formation, because of the implicit geometric constraints in the micropores, the lower water concentration, and the decreased tar formation associated with high methanol concentrations. This could have significant reactor design implications, as the results obtained here suggest that the reaction should be terminated after approximately 30 minutes to maximise hydroquinone production (under the conditions evaluated in these experiments), even though the corresponding phenol conversions are low (ca. 10 mol-%). The higher hydroquinone selectivities reached at low phenol conversions for the discrete peroxide addition experiments also confirm this. Practically, to enhance the hydroquinone selectivity for reaction over TS-1, the initial phenol-peroxide molar ratio should be ca. 10, methanol should constitute not less than 90 vol-% of the reaction volume, and the peroxide should be added in discrete amounts. For reaction over Al-free Ti-Beta, methanol solvent also enhances the hydroquinone formation as expected. At low phenol conversions (ca. 10 mol-%) hydroquinone is still the preferred product, although in contrast to TS-1 the selectivity increases with phenol conversion, and is higher with higher initial peroxide concentrations. Under the best conditions evaluated here for optimal hydroquinone formation, the initial phenol-peroxide molar ratio should be ca. 2.5, with methanol making up at least 90 vol-% of the total volume. Discrete peroxide addition in methanol solvent for the Al-free Ti-Beta catalysed hydroxylation gives excellent improvements in hydroquinone selectivity (2.5 times higher than water solvent), and the addition in more discrete portions might further improve hydroquinone formation, and should therefore be examined.

The scope of this dissertation work is a description of modern methods of reducing exhaust emission in diesel engines. The fundamental part is the application of these methods for diesel engines for off-road use that means for engines that are used in tractors and road machines. The mentioned evidence for the practical utility of the results of this dissertation thesis in practice and their verification on the actual engine are given in the conclusion.

The aim of this thesis is the study of application of the synergistic effects of various advanced oxidation processes (AOP) used for decomposition of chemical compounds resistant to biodegradation. The synergistic effect of photocatalytically active material and low temperature plasma were tested in my thesis. Model substances with photocatalytically active material were exposed to atmospheric plasma discharge (Gliding Arc) in order to improve generation of the active hydroxyl groups and oxidation processes. The first chapter of the theoretical part summarizes the knowledge of advanced oxidation processes, their principles and utilization. Next chapters are dedicated to basic summary of titanium dioxide and types of creating the thin films. The last part of theoretical chapter describes the types of plasma discharges. The experimental part describes the equipment for decomposition of chemical compounds resistant to biodegradation using AOP. Next chapter of the experimental part is dedicated to decomposition of organic dye AO7 and antibiotic Verapamil hydrochloride. The last chapter summarizes the results of the experiments.

This diploma thesis aims to optimalization the process of magnetron sputtering and creating of thin layers for use in advanced oxidation processes. During the work was created range of TiOx layers. For this process was used physical method of sputtering called PVD. The photocatalytic activity of the deposited films was tested by degradation of organic dyes Acid Orange 7. Furthermore, the layer was analyzed on surface morphology (SEM) and the layer thickness (profilometry). Study of created layers was focused on the link between the characteristics of each layer, deposition parameters and photocatalysis properties. Based on these results, the layers were applied in a system using AOP for the decomposition of organic substances. The first chapter is devoted to a summary of existing knowledge of photocatalysis and its principles. Another chapter is devoted to the theory and methods of applying thin layers and summary of knowledge of the low-pressure discharges. In the exprimental section there are described various components of the apparatus. Furthermore, the experimental part of the work focuses on the analysis of the optimization process of applying thin layers on titanium oxide. The last chapter of the thesis contains the results of the experiments on the basis of is designed another research progress of this issue.

This thesis is focused on the study of glycosphingolipids in the rat liver in different types of cholestasis and the effect of oxidative stress on changes in the composition and localization of gangliosides. First, it was necessary to optimize the immunochemical detection of glycosphingolipids. GM1 ganglioside was selected as a representative of a large glycolipid family. We found that minimum water content in the fixing solution was a key condition for fixation of histological sections. Optimized method of GM1 detection was subsequently used in in vivo experiments. We have demonstrated that estrogen-induced cholestasis characterized by high concentrations of bile acids and increased oxidative stress caused changes in the synthesis and distribution of liver gangliosides. HMOX induction is associated with a reduction in oxidative stress level and accompanied by normalization in GSL content. In experiments with obstructive cholestasis, we found that changes in the distribution and synthesis of gangliosides were not strictly specific to a particular type of cholestasis. We assume that it represents a general mechanism of hepatoprotection. We also confirmed the important role of bilirubin, product of HMOX reaction, in protection of hepatocytes against oxidative damage caused by high concentrations of...

碩士
國立中興大學
環境工程學系所
96
In situ chemical oxidation (ISCO) is an alternative to remediate soil and groundwater. Sodium peruslfate (Na2S2O8), a strong oxidant with a redox potential of 2.01 V, is recently used for ISCO. It has been postulated that persulfate anion can be thermally activated to produce a powerful oxidant known as the sulfate radical (SO4-•), which can potentially destroy organic compounds. Under alkaline condition, the sulfate radical can proceed radical interconversion reaction with hydroxyl ions to generate the hydroxyl radical (HO•). As sulfate and hydroxyl radicals are possibly simultaneously present or either one can prevail over the other during the activated persulfate process depending on solution conditions (especially pH), SO4-• and HO•present different reactivities towards organic contaminants. Therefore, the objective of this research focuses on identifying the sulfate and hydroxyl radicals produced from persulfate activation under different pH conditions. It is difficult to measure or identify SO4-• and HO• because short half-lives of two radicals. The chemical probe technique was attempted for identifying the radical produced in the thermal persulfate activation system. Due to the differences of their reaction rates between SO4-• and HO•, tert-butyl alcohol (TBA), nitrobenzene (NB) and phenol were selected as chemical probes. Experimental results revealed that TBA can be degraded with the sulfate radical, but also with persulfate anion. Therefore, TBA may not be a suitable chemical probe. However, NB and phenol were demonstrated to react only with radical oxidants and application as chemical probes. Furthermore, the reaction orders with respect to persulfate and chemical probe (NB and phenol) are nearly 1 and 0, respectively. The results of radical identification experiments revealed that the degradation rate of NB at pH = 2, 4 and 7 is much slower than those at pH = 9 and 12. For example, the degradation rates at pH = 9 and 12 were increased by 13.8% and 388%, respectively, comparing to that at pH = 2. Because the reaction rate constant between NB and HO• is higher than that between NB and SO4-•, it can be deduced that the concentration of HO• increased when pH was increased for pH = 9 and HO• would be the major radical oxidant. On the other hand, it was observed that the degradation rate of phenol are faster than that of NB under pH = 2, 4 and 7. The reaction rates between phenol and SO4-•/HO• have been reported at near diffusion rates (109 M-1s-1). When comparing reactions of SO4-•/HO• towards NB and phenol, it can be conducted that under neutral and acidic conditions, SO4-• is the major radical oxidant species.

The aim of this diploma thesis is deposition of TiO2 thin films onto different types and sizes of substrates, and some of these layers dope by iron or silver. During the work was range of TiO2 layers created using a method of physical vapor deposition namely magnetron sputtering. For these processes was chosen the Dreva ARC 400 Hard Material Coating Plant device. The main aim of these depositions was to attempt to create TiO2 thin films on a substrates of larger surface than its in average laboratory processes usual. For this purpose were TiO2 layers deposited onto square glass plates of side length 10 cm. For comparsion and analysis were also as a substrates used microscope slides and fragments of silicon wafers. These substrates were used for testing of photocatalytic activity and on surface morphology (SEM). The theoretical part of this thesis aims to a methods of deposition TiO2 layers and their characteristics. In the experimental part is the used coating equipment and parameters of each deposition process described. Further the characteristics and results of individual experiments are described.

Solution combustion synthesis (SCS) with its origin at IPC department of IISc has been widely practiced for synthesis of oxide materials. It is simple and low cost process, with energy and time savings that can be used to produce homogeneous, high purity, uniformly doped, nano crystalline ceramic powders. The powders characteristics such as crystallite size and surface area are primarily governed by enthalpy, flame temperature of combustion, fuel and fuel to oxidizer ratio ( F/O). In the present work an attempt has been made to investigate the process in order to exercise a control over the phase formation and nature of the product. Initial part of the work deals with the effect of fuel to oxidizer ratio on the powder properties of binary oxides with urea as fuel. The variation of adiabatic flame temperatures are calculated theoretically for different F/O ratios according to thermodynamic concept and correlated with the observed flame temperatures. Difference in the measured flame temperature and theoretical flame temperature in the fuel rich region is explained on the basis of incomplete combustion model. The effect of decomposition temperature difference of fuel and oxidizer, solubility of reactants on exothermicity of combustion reaction taking aluminiumnitrate system for various fuels is investigated. The effect of mixed fuel approach is studied by using the urea-glycine mixed fuel system using aluminium nitrate as oxidizer and employed for successful synthesis of the gamma alumina. Further Compaction behavior of SCS nano ceramic powders is studied by using Universal testing machine and the effect of F/O ratio, on agglomeration strength, aggregation strength of powder is investigated. Very few reports can be found on usage of SCS ceramic powder for biomaterial applications. By using these investigations a pyroxene series Diopside (CaMgSi2O6) silicate material is synthesized by SCS. Effect of different fuels on Diopside (DP) phase formation is investigated. Finally the DP and DP-ZnO composites, made by using Uniaxial hot pressing are investigated for their antibacterial, cytocompatibility properties. Antibacterial activity of E.Coli bacterium of Diopside powders was dose dependent type. Results of the bioactivity investigations shown flattened MC3T3 mouse osteoblast cells and MC C2C12 Myoblast cells and linkage bridges formed between them on Diopside and DP-ZnO surfaces show cyto compatibility and MTT results showed that percentage of ZnO needs to be tailored between 0-10 in order to achieve maximum cytocompatibility coupled with antibacterial property.