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.

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.

A associação dos métodos cinéticos de análises e dos sistemas de análises em fluxo foi demonstrada em relação à determinação espectrofotométrica de ferro e vanádio em ligas Fe-V O método se baseia na influência de Fe2+ e VO2+ na taxa de oxidação de iodeto por dicromato sob condições ácidas; por esta razão o emprego do redutor de Jones foi necessário. Um sistema de análises por injeção em fluxo (FIA) e um sistema multi-impulsão foram dimensionados e avaliados. Em ambos os sistemas, a solução da amostra era inserida no fluxo transportador / reagente iodeto, e a solução de dicromato era adicionada por confluência. Sucessivas medidas eram realizadas durante a passagem da zona de amostra processada pelo detector, cada uma relacionada a uma diferente condição para o desenvolvimento da reação. O tratamento dos dados envolveu calibração multivariada, particularmente o algorítmo PLS. O sistema FIA se mostrou pouco adequado para as determinações multi-paramétricas, uma vez que os elementos de fluído resultantes da natureza de escoamento laminar não continham informações cinéticas suficientes para compor as etapas de modelagem. Por outro lado, MPFS mostrou que a natureza do fluxo pulsado resulta em melhorias nas figuras de mérito devido ao movimento caótico dos elementos de fluído. O sistema proposto é simples e robusto, capaz de analisar 50 amostras por hora, significando em um consumo de 48 mg KI por determinação. A duas primeiras variáveis latentes contém ca 94 % da informação analítica, mostrando que a dimensionalidade dupla intrínsica ao conjunto de dados. Os resultados se apresentaram concordantes com aqueles obtidos por espectrometria de emissão optica com plasma induzido em argônio. / Differential kinetic analysis can be implemented in a flow system analyser, and this was demonstrated in designing an improved spectrophotometric catalytic determination of iron and vanadium in Fe-V alloys. The method relied on the influence of Fe2+ and VO2+ on the rate of the iodide oxidation by Cr2O7 under acidic conditions; therefore the Jones reductor was needed. To this end, a flow injection system (FIA) and a multi-pumping flow system (MPFS) were dimensioned and evaluated. In both systems, the alloy solution was inserted into an acidic KI solution that acted also as carrier stream, and a dichromate solution was added by confluence. Successive measurements were performed during sample passage through the detector, each one related to a different yet reproducible condition for reaction development. Data treatment involved multivariate calibration by the PLS algorithm. The FIA system was less recommended for multi-parametric determination, as the laminar flow regimen could not provide suitable kinetic information. On the other hand, a MPFS demonstrated that pulsed flow led to enhance figures of merit due to chaotic movement of its fluid elements. The proposed MPFS system is very simple and rugged, allowing 50 samples to be run per hour, meaning 48 mg KI per determination. The first two latent variables carry ca 94 % of the analytical information, pointing out that the intrinsic dimensionality of the data set is two. Results are in agreement with inductively coupled argon plasma – optical emission spectrometry.

A associação dos métodos cinéticos de análises e dos sistemas de análises em fluxo foi demonstrada em relação à determinação espectrofotométrica de ferro e vanádio em ligas Fe-V O método se baseia na influência de Fe2+ e VO2+ na taxa de oxidação de iodeto por dicromato sob condições ácidas; por esta razão o emprego do redutor de Jones foi necessário. Um sistema de análises por injeção em fluxo (FIA) e um sistema multi-impulsão foram dimensionados e avaliados. Em ambos os sistemas, a solução da amostra era inserida no fluxo transportador / reagente iodeto, e a solução de dicromato era adicionada por confluência. Sucessivas medidas eram realizadas durante a passagem da zona de amostra processada pelo detector, cada uma relacionada a uma diferente condição para o desenvolvimento da reação. O tratamento dos dados envolveu calibração multivariada, particularmente o algorítmo PLS. O sistema FIA se mostrou pouco adequado para as determinações multi-paramétricas, uma vez que os elementos de fluído resultantes da natureza de escoamento laminar não continham informações cinéticas suficientes para compor as etapas de modelagem. Por outro lado, MPFS mostrou que a natureza do fluxo pulsado resulta em melhorias nas figuras de mérito devido ao movimento caótico dos elementos de fluído. O sistema proposto é simples e robusto, capaz de analisar 50 amostras por hora, significando em um consumo de 48 mg KI por determinação. A duas primeiras variáveis latentes contém ca 94 % da informação analítica, mostrando que a dimensionalidade dupla intrínsica ao conjunto de dados. Os resultados se apresentaram concordantes com aqueles obtidos por espectrometria de emissão optica com plasma induzido em argônio. / Differential kinetic analysis can be implemented in a flow system analyser, and this was demonstrated in designing an improved spectrophotometric catalytic determination of iron and vanadium in Fe-V alloys. The method relied on the influence of Fe2+ and VO2+ on the rate of the iodide oxidation by Cr2O7 under acidic conditions; therefore the Jones reductor was needed. To this end, a flow injection system (FIA) and a multi-pumping flow system (MPFS) were dimensioned and evaluated. In both systems, the alloy solution was inserted into an acidic KI solution that acted also as carrier stream, and a dichromate solution was added by confluence. Successive measurements were performed during sample passage through the detector, each one related to a different yet reproducible condition for reaction development. Data treatment involved multivariate calibration by the PLS algorithm. The FIA system was less recommended for multi-parametric determination, as the laminar flow regimen could not provide suitable kinetic information. On the other hand, a MPFS demonstrated that pulsed flow led to enhance figures of merit due to chaotic movement of its fluid elements. The proposed MPFS system is very simple and rugged, allowing 50 samples to be run per hour, meaning 48 mg KI per determination. The first two latent variables carry ca 94 % of the analytical information, pointing out that the intrinsic dimensionality of the data set is two. Results are in agreement with inductively coupled argon plasma – optical emission spectrometry.