Gasification of biomass is a one of the several technologies for energy production from biomass. Biomass is a promising renewable source of energy and is in a centre of attention of energy industry not only in the Czech Republic, but also in the EU and in the world. Gasification is a thermo chemical transformation of fuel with access of understoicheiometric amount of oxidizer which produces gas of low heating value. Its main combustible components are hydrogen, carbon dioxide and methane. Produced gas may be further used in power and heating plants. Besides combustible and neutral components, gas also contains pollutants such as sulphur compounds, chlorine compounds, ash and tar. It is tar which is considered to be the underbelly of gasification as it causes, along with ash, fouling in transport tracks and terminal equipment, and blocks direct application of gas. This dissertation thesis presents design of filter for elimination of tar from the gas generated in fluid gasification equipment. This work is closely related to current research at Energy Institute at Faculty of Mechanical Engineering at Brno University of Technology. First part deals with theoretical background of this issue. Biomass properties are mentioned in relation to gasification. Types of gasification equipment are described and principle of gasification including chemical reactions is given in detail. Special part is dedicated to pollutants in the gas, especially to production of tar and its properties, which is important for consequent work. Main focus is on possibilities of catalytic cleaning of gas from tar. Principle of tar decomposition is described and types and properties of catalysts are given. Part of the thesis tackles the issue of real operations and loss of efficiency of catalyst due to sulphur compounds, sintering and carbon fouling. Based on experience and analysis in the first part of the thesis, concept of elimination of tar from gas was laid out. In addition to that, method for measurement at Biofluid 100 experimental unit was outlined and filter for testing of industrial catalysts using metal was designed. Series of experiments were further conducted in order to find out efficiency of three opted catalysts for tar decomposition. Results of these experiments are described in detail and assessed in the conclusion of this thesis which also contains outline for economic assessment of method of gas cleaning using catalysts.

This diploma thesis follows the degradation of inkjet print by ultraviolet radiation and ozone effect for different types of papers. Colour test charts for the evaluation of accelerated ageing effect of ultraviolet light and gas fading were designed. These test charts were printed by dye-based inks on selected receiving media and exposed to ozone-enriched environment, UV radiation and their combination. The colorimetric values L* a* b* were calculated from spectral data of all patches of the test charts. The ozone effect on the prints was evaluated in the terms of total colour difference and dye concentration. The degradation of dye caused by ozone was observed also in a long-term period, after the contact of sample with ozone was terminated. Results of printed samples accelerated ageing by UV radiation and those that were influenced by the ozone effect were evaluated in the same way. It was found out that UV radiation and ozone treatment have a different effect on the degradation of dyes. The degradation rate is also strongly influenced by the receiving layer composition of papers used for inkjet printing. Also the catalytic effect of dyes was evaluated.

Palladium catalysts are frequently used in C-C coupling reactions. The aim of this work is to prepare several heterogeneous palladium catalysts from comercially available silica gel, each with different bifunctional ligand deposited on the surface of silica gel by N-propylamide linking group, and their testing on several C-C coupling reactions (Heck reaction, reaction of acyl chlorides with boronic acids and reaction of acyl chlorides with terminal acetylenes). Some other aspects of heterogeneous catalysis (such as palladium leaching into the reaction mixture and possibility of catalyst reuse) are discussed, too. Powered by TCPDF (www.tcpdf.org)

In this thesis, we present the investigation of influence of methanol crossover, which significantly decreases the performance of DMFC (Direct Methanol Fuel Cell). Additionally the poisoning effect occurs on the cathode side. The durability of cathode catalyst exposed by methanol vapor is studied. Moreover, the regene- rative behavior after exposition has been found. The comparison of commercial catalyst with our own sputtered Pt and PtCo and PtRu thin layers as cata- lyst is presented. Obtained results have shown that PtCo is reasonable compro- mise between pure Pt, which has high performance, and PtRu, which is tolerant to methanol poisoning. Future research should further evaluate the advantages of PtCo cathode catalyst prepared by standard procedures and its market poten- tial in comparison with PtRu. 1

This thesis presents specification and implementation of a system for detection of enzymes in metagenomic data. The detection is based on a provided enzyme sequence and its goal is to search the metagenomic sample for its novel variants. In order to guarantee that found enzymes truly have the desired catalytic function, the system employs a number of catalytic function verification methods. Their specification, implementation and evaluation is one of the main contributions of this thesis. Experiments have shown, that proposed methods reach sensitivity as high as 89%, specificity of 95%, values of AUC metric above 0.9 and average throughput of 1,203 verifications per second on regular personal computer. Evaluation of the system also led to discovery of a partial sequence of novel haloalkane dehalogenase enzyme in a metagenomic sample from soil. The implementation is able to work on a personal computer as well as on a grid computing environment.

Disertation thesis deals with development of hot dolomite filter for the purposes of cleaning of gas polluted by biomass and waste gasification with ash and tar as well as sulphur and chlorine compounds as main pollutants. Gas is then cleaned so that it can be utilized in cogeneration units with combustion engines. This supports advancement of gasification techniques using decentralized power and heat generation especially for design of small scale units. Concrete aims of this thesis are stated in chapter 2. Experimental fluid gasification stend Biofluid 100 has been in operations at Brno University of Technology (BUT) since 2000 and it helps research of biomass and waste gasification. Development of the filter initially utilized needs and experience with the utility during cooperation of BUT and ATEKO Hradec Králové. Water scrubber was used for gas cleaning, however, this method proved to be ineffective. Alternative solutions were considered. Based on literature search, natural catalysts with limestone basis were opted. First part of the thesis presents literature search of this issue. Historic development and description of gasification process are briefly discussed as well as elementary classification of gasification generators. This part is followed by chapters dealing with gas pollutants. Tar – the most significant pollutant – is discussed in a separate chapter which presents tar formation, its classification, characteristics and methods for its removal. Brief summary of requirements on gas properties with respect to its utilization in various applications (especially in cogeneration units) follows. Other part of the literature search part focuses on methods of removal of tar from gas, especially on catalyst methods. Dolomite characteristics, description of dolomite calcination as well as simplified kinetic model of tar cracking using dolomite are presented. Based on literature search, laboratory and verification equipment was designed for the purposes of dolomite properties testing. Equipment description as well as description of experimental stend Biofluid 100 where the experimental tests were carried out can be found in introduction of the experimental part. This is followed by a complete description of pilot equipment design of hot dolomite filter with general description of experimental work process, brief characteristics of the fuel and catalytic material used. Final part of the work comprises of experiment results that were carried out on the pilot equipment. Focus is on efficiency of tar removal in connection with operation temperature, amount of catalytist and material used. Influence of these parameters on gas composition and energy intensity of the whole process under these conditions is mentioned as well. Possibility of autonomous unit operations without electricity heating is briefly outlined. Summary of the most significant results including the potential of future hot dolomite filter development is stated the final part of the thesis.

Title: Synthesis and catalytic properties of phosphinoferrocene guanidine Author: Ondřej Bárta Institution: Faculty of Science, Charles University in Prague, Department of Inorganic Chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Polar phosphine ligands proved to be useful in homogeneous and biphasic catalysis. Most of these phosphines bears anionic functional groups. On the other hand, functionalization of phosphines by cationic substituents is still quite uncommon, although these functional groups possess properties that could improve catalytic performance of the catalyst. In this regard, nitrogenous bases are particularly attractive due to their inherent basicity and the ability to enter into hydrogen bonding interactions. This thesis describes the synthesis of a novel ferrocene-based phosphine functionalized with guanidine moiety, viz. N-[1′-(diphenylphosphino)ferrocenylmethyl]guanidine (3). This compound was obtained by direct guanylation of 1′-(diphenylphosphino)- 1-(aminomethyl)ferrocene (2) (see scheme). Compound 3 was further used to prepare palladium complexes including the unusual zwitterionic complex [PdCl3(3H)]. The molecular structures of the prepared complexes were determined by X-ray diffraction analysis. Catalytic properties of phosphine 3 and complex [PdCl3(3H)] were...

Title: Palladium catalysts deposited over novel siliceous supports Author: Pavlína Křečková Department: Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Supervisor's e-mail address: stepnic@natur.cuni.cz Advisor: prof. Ing. Jiří Čejka, DrSc. Advisor's e-mail address: jiri.cejka@jh-inst.cas.cz Abstract Keywords: palladium; deposited catalysts; siliceous supports; C-C coupling reaction. The aim of this work was to prepare a deposited palladium catalyst from Pd2+ and twodimensional zeolite ITQ-2 bearing ≡SiCH2CH2CH2NHCH2CH2NEt2 groups at the surface. This catalys has been evaluated in the Heck reaction between n-butyl-acrylate and brombenzene to give n-butyl-cinnamate. Influence of the reaction temperature, the solvent, base and hydrate water on the progress of the Heck reaction was investigated. This work also deals with the possibility of recycling the catalyst and, due to its nature, with the quantity of leached palladium into the reaction mixture. Furthermore, the work describes differences in morphology between the fresh and a recycled catalyst.

Disertation thesis deals with development of hot dolomite filter for the purposes of cleaning of gas polluted by biomass and waste gasification with ash and tar as well as sulphur and chlorine compounds as main pollutants. Gas is then cleaned so that it can be utilized in cogeneration units with combustion engines. This supports advancement of gasification techniques using decentralized power and heat generation especially for design of small scale units. Concrete aims of this thesis are stated in chapter 2. Experimental fluid gasification stend Biofluid 100 has been in operations at Brno University of Technology (BUT) since 2000 and it helps research of biomass and waste gasification. Development of the filter initially utilized needs and experience with the utility during cooperation of BUT and ATEKO Hradec Králové. Water scrubber was used for gas cleaning, however, this method proved to be ineffective. Alternative solutions were considered. Based on literature search, natural catalysts with limestone basis were opted. First part of the thesis presents literature search of this issue. Historic development and description of gasification process are briefly discussed as well as elementary classification of gasification generators. This part is followed by chapters dealing with gas pollutants. Tar – the most significant pollutant – is discussed in a separate chapter which presents tar formation, its classification, characteristics and methods for its removal. Brief summary of requirements on gas properties with respect to its utilization in various applications (especially in cogeneration units) follows. Other part of the literature search part focuses on methods of removal of tar from gas, especially on catalyst methods. Dolomite characteristics, description of dolomite calcination as well as simplified kinetic model of tar cracking using dolomite are presented. Based on literature search, laboratory and verification equipment was designed for the purposes of dolomite properties testing. Equipment description as well as description of experimental stend Biofluid 100 where the experimental tests were carried out can be found in introduction of the experimental part. This is followed by a complete description of pilot equipment design of hot dolomite filter with general description of experimental work process, brief characteristics of the fuel and catalytic material used. Final part of the work comprises of experiment results that were carried out on the pilot equipment. Focus is on efficiency of tar removal in connection with operation temperature, amount of catalytist and material used. Influence of these parameters on gas composition and energy intensity of the whole process under these conditions is mentioned as well. Possibility of autonomous unit operations without electricity heating is briefly outlined. Summary of the most significant results including the potential of future hot dolomite filter development is stated the final part of the thesis.

Due to the continuous growth of energy consumption it is required that development in the energy sector is focused on renewable energy sources. Another possibility how to reduce the consumption of primary energy resources is also searching for new and non-traditional fuels. The biomass is the best and potentially expandable renewable energy source in geographic conditions in the Czech Republic. The energy usage of biomass has experienced a significant increase in recent years, however, even in the big energy power plant. This increase in consumption made mainly from wood biomass a shortage fuel, and it began to raise its price. The consumers of biomass fuel are starting to look for a different type of fuel at this time. Stalk and slightly contaminated biomass are representatives of these non-traditional fuels. Stalks are mostly annual plants grown primarily for subsistence. Waste parts of these plants can be utilized for production of energy. The characteristic temperatures of stalk ash have relatively low values. Sintering of ash in a device is one of the obstacles for energy usage of stalk. Sintering of ash brings a number of operational problems at power facilities. Therefore, the part of a research is dedicated to the melting of ash. The thermal gasification is one of the possibilities how to use biomass efficiently. Gasification can be understood as the thermo-chemical conversion of solid fuel into a different state, in this case the gaseous state. The combustion process is generally more manageable for gaseous fuels. Due to this process ower emissions of undesirable compounds at the output of the combustion device can be achieved. Thermal gasification process takes place under stochiometric access of oxidant. The gas with low heating value is on the outlet from gasification process. The main components of produced gas are hydrogen, carbon monoxide and methane. The final gas contains also a lot of undesirable constituents, which make this gas disadvantaged in energy. These constituents are neutral components that dilute gas only, and pollutants as dust, tar and compounds of sulfur and chlorine. These pollutants complicate further use of the generated gas. The tar compounds together with dust causing build-up on the conveyor pipe and also on the combustion equipment, which are using this generated gas. The quality of produced gas is increases by another reprocessing and cleaning. The purified gas can be used for cogeneration of energy and burn it in internal combustion engines or gas turbines. Other possibility is typical usage for heating according to the needs of technology. The atmospheric fluidized bed gasification reactor Biofluid 100th was built for experimental purposes in the laboratories of the Energy Institute. The thesis is focused on thermal gasification of stalk and other non-traditional fuels in Biofluid device. The aim is to achieve a stable gasification process of stalk and thereby verify the possibility of stalk use as fuel for technology Biofluid. Subsequent aim is design of methods for cleaning the raw gas from the tar compounds. The research is focused on the secondary gas cleaning methods due to the requirements of high purity of the resulting gas.