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Catalytic oxidation of VOC on commercially available catalysts
Osička, Tomáš ; Jecha, David (referee) ; Brummer, Vladimír (advisor)
The main topic of this thesis is a catalytic oxidation which belongs to a group of modern technologies for removing emission of CO and VOC from waste air. In the introduction of this thesis, the basic concepts are defined. Further the legislative requirements associated with VOC emissions, emission limits and conditions are summarized. Described destructive and non-destructive methods for removing VOCs from waste gases are also briefly described. Increased attention is paid to the catalytic oxidation as the main theme of the thesis. It was searched for industrial applications where the catalytic oxidation is used. Another chapter is devoted to the theoretical analysis of kinetics of catalytic oxidation reactions. Firstly, the basic types of reactors are described and also material balance and reaction rate for the isothermal and adiabatic reactor. In the experimental part results of performed kinetic measurements on a pilot unit for catalytic commonly used organic solvents (VOCs) using commercially available catalysts were summarized. Pre-exponential factors and activation energies for sprinkling catalysts EnviCat VOC-5565 and EnviCat 55068 for substances ethanol, toluene and acetone were determined. "Light-off" curves for these substances and methane were measured and on sprinkled catalyst EnviCat 55068 and on monolithic catalyst Purelyst PH-304.
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Kinetics of the Coordination Polymerization of -olefins Catalyzed by Nickel Diimine Complexes
Peleška, Jan ; Kratochvíla, Jan (referee) ; Pinkas,, Jiří (referee) ; Petrůj, Jaroslav (referee) ; Cihlář, Jaroslav (advisor)
This Ph.D. thesis is focused on kinetic study of propene and hex-1-ene coordination polymerizations initiated by complex [(2-tBuC6H4)N=C(1,8-naphtalenediyl)C=N(2-tBuC6H4)]NiBr2 activated by simple organoaluminium compounds and on product properties. In first three parts proper activators are chosen in model polymerizations. The attention is paid to the reproducibility of polymerizations and analytical methods. The fourth part is focused on propene polymerization kinetics with the aim to define optimal reaction conditions, especially polymerization temperature and time. The four part concerns also properties of polymers. The fifth and sixth parts deal with hex-1-ene polymerization kinetics conducted at various activator/initiator molar ratios and various catalytic precursor concentrations, to find out kinetic orders with respect to catalyst and cocatalyst concentration. Last part is oriented on detail mechanistic investigation of nickel diimine complexes activation process. Results of measurements in presence or absence of monomer enabled to propose new interpretation of UV-vis spectra based on concrete structures of absorbing species.
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Kinetics of photochromic reactions in thin polymeric layers
Zeman, Vojtěch ; Weiter, Martin (referee) ; Vala, Martin (advisor)
The thesis is aimed to the study of spiropyrane behavior in polymeric matrix of poly(N-vinylkarbazole) (PVK) and poly[2-methoxy-5-(3´,7´-dimethyloctyloxy)-1,4-fenylenvinylene)] (MDMO-PPV). The photochromic transformation of spiropyrane to its isomeric merocyanine form (SPMC) was studied by absorption and emission spectroscopy. It was found, that photochromic reaction is markedly dependent on the environment. In the PVK polymer, which don’t absorb in the visible region, a high yield of photochromic reaction was achieved. Both, absorption and emission spectrums were observed for this system. From the measurement of time dependencies of the fotochromic reaction, the activation energy of the reverse reaction was determined. A different behavior, particularly in emissive spectrums, was found for the MDMO-PPV polymer doped with spiropyrane. Instead of formation of new band of merocyanine, decrease of the polymer fluorescence was observed. Subsequently, we studied the interaction between the polymeric matrix and the photochromic spiropyrane using fluorescence quenching method. On the basis of energy transfer theory, a critical radius of the fluorescence quenching sphere in solution and in solid was determined.
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Synthesis of Mineral Oils by Oligomeration of 1-alkenes
Porubský, Tomáš ; Kučera, František (referee) ; Petrůj, Jaroslav (advisor)
The theoretical part presents a summary of existing information and procedures for the oligomerization of 1 alkenes. It also introduces suggestion of the new method for preparing poly(1-hexene) by controlled or living polymerization with nitroxyl radicals. In the experimental part was synthesized oligomer of 1-hexene with DBP or AIBN radical initiators and coordination Ziegler-Natta catalysts, which consisted of TiCl4 and organometallic compounds TIBA or TNHA. GC/MS analysis of the radical polymerization reaction mixture, showed no oligomer formation even after 6 hours. Effect of Ti/Al ratio, temperature and type of organoaluminium compund on conversion and molecular weight were investigated. Reaction products were analyzed by 1H NMR and GC/MS spectrometry. Results showed that the obtained oligomer was a mixture of oligomers with a degree of polymerization 2-9 and average molecular weight of 220-270 g/mol. Monomer conversion reached values of 72 98 %.
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Automated measurement system for ethene polymerization
Janošík, Zdeněk ; Richtera, Lukáš (referee) ; Přikryl, Radek (advisor)
Thanks to macromolecular chemistry development polymers become essential materials for wide range of applications. Research of catalytic systems used for production of polymers plays a key role in development of new polymer-based materials. The aim of this work was to develop system providing automated kinetic measurement of catalytic systems used in ethylene solution polymerization. The theoretical part of the thesis provides basic overview on chemical process taking part in ethylene polymerization and technical instruments used for its automation. Description of the devised system, its technical solutions and performed experiments used for verification its proper function are presented in the experimental part. Acquired data were compared with published results obtained with the same catalytic systems. Texts are accompanied by schemes, screenshots and photos.
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Extraction of beta-Sitosterol from the Stinging Nettle Root with Supercritical CO2
Sajfrtová, Marie ; Bártlová, Milena ; Sovová, Helena
The stinging nettle root contains both polar and non-polar biologically active substances. beta-Sitosterol (BS), the most important component of its neutral lipids, is active in the root extracts used for various alternative medicine treatments, including the reduction of enlarged prostate. Dry roots contaning 0.28 g/kg BS were extracted with CO2 at pressure 12-60 MPa and temperature 40-80 C. Though the maximum yield of BS was only 89 %, its concentration in extract was increased by 13 % compared to the extraction with hexane. Changing vials where the CO2 extract was collected, fractions with double and higher BS concentration could be obtained. The fractionation was simulated using a mathematical kinetic model of multicomponent extraction.
Fulltext: content.csg -  PDF
Plný tet: SKMBT_C22013110513041 - PDF
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Kinetics and temperature dependance of cellulose degrading enzymes in the Arctic soils
VAZAČ, Jan
Kinetics and temperature dependance of ?-glucosidase and cellobiosidase was investigated in Arctic soil. These enzymes are key in cellulose degradation, while ?-glucosidase produces the final product of cellulose degradation, the glucose, which si readily available to soil microbes and can influence the CO2 production. The enzymes activities was measured using fluorogenic substrates.
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Differences in CO2 Extraction of Vegetable Oils, Essential Oils, and Minor Components from Plants
Sovová, Helena
Significant progress in understanding the phenomena that control supercritical fluid extraction from plants was made in the last years and is reflected in the literature. Combination of chemical engineering approach and botanical knowledge has appeared to be fruitful for the choice of extraction model and even for the prediction of extraction kinetics. This contribution refers to the papers utilizing knowledge of plant microstructure and location of extracted substances together with extraction equilibrium and attempts to specify the differences among extraction kinetics of vegetable oils, essential oils, and other substances. The most abundant substances like vegetable oils in seeds can be regarded in first approximation as non-interacting with plant matrix, in contrast to the minor components whose equilibrium concentration in CO2 is affected by their adsorption on matrix and often also by co-extracted substances.
Fulltext: content.csg - PDF
Plný tet: SKMBT_C22012102414100 - PDF
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A Simplified Calculation of a Continuous Flow Packed Contactor with Help of Characteristic Times
Sovová, Helena
The proposed approach is illustrated on several examples of supercritical fluid extraction kinetics. Simple expressions for the calculation of characteristic times of both extraction and individual extraction steps are derived from mass balance equations and applied on experimental data from typical extractions from plants with supercritical CO2, as the extraction of oils from seeds or the extraction of essential oils from aromatic plants.
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