Biomass gasification is a promising technology for conversion of various biomass feedstocks to producer gas for subsequent production of fuels and chemicals. A dual fluidised bed (DFB) steam gasifier is used in the present research to produce the producer gas for Fischer-Tropsch (FT) liquid fuel synthesis. However, NH3 and H2S gases in the producer gas remain an issue to be resolved because they are poisonous to the catalysts employed in the FT reactor. To remove NH3 and H2S, two methods were investigated in this research: (1) primary measures which were employed in the DFB steam gasifier including process optimisation and application of bed materials for catalytic NH3 decomposition and H2S adsorption; and (2) secondary measures or downstream cleaning methods after the gasifier. The combination of the primary measures and the secondary measures is an effective way to remove the NH3 and H2S in the producer gas from gasification process. Studies on the primary measures were divided into two parts. In the first part, in situ reduction of NH3 and H2S in biomass producer gas from the DFB steam gasifier was performed. The primary measures consisted of optimisation of operation conditions and application of bed materials. The main operation conditions in the DFB steam gasifier studied were gasification temperature, steam to fuel (S/F) ratio, and mean gas residence time (f). The bed materials tested include silica sand, iron sand (ilmenite), and calcined olivine sand. For the second part of the primary measures, an influence of the lignite to fuel (L/F) ratio on NH3 and H2S concentrations and conversions in co-gasification of blended lignite and wood pellets in the DFB steam gasifier was investigated. Experiments were performed in the DFB steam gasifier at 800C with blended lignite and radiata pine wood with the L/F ratio ranging from 0% to 100%. It was found that all of the studied parameters including gasification temperature, S/F ratio, f, bed material, and L/F ratio significantly influenced the NH3 and H2S concentrations and conversions in the producer gas. For the secondary measures, a novel hot catalytic reactor and adsorber was developed in the present research for the simultaneous removal of NH3 and H2S. In a hot gas reactor operated at 500-800C and under atmospheric pressure, titanomagnetite was tested for NH3 and H2S removal by hot catalytic NH3 decomposition and H2S adsorption reactions. Titanomagnetite was tested with three different gas streams including 2,000 ppmv NH3 in Ar, 2,000 ppmv NH3 and 230 ppmv H2S in Ar, and 2,000 ppmv NH3 and 230 ppmv H2S in simulated biomass producer gas. From the experimental results, it was discovered that ferrite (α-Fe) readily formed by the H2 reduction of titanomagnetite has shown almost complete NH3 decomposition (100%) in Ar gas at 700 and 800C. The presence of H2S in the gas mixture of NH3 and Ar slightly reduced the catalytic activity for NH3 decomposition at 700 and 800C (>96%) and H2S adsorption of more than 98% could be achieved at the same temperature range. However, in the test with simulated biomass producer gas, 60% NH3 decomposition and 9% H2S adsorption were obtained at 800C, whereas 40% NH3 decomposition and 80% H2S adsorption were obtained at 500C. The decrease of NH3 decomposition and H2S adsorption at 800C in simulated biomass producer gas could be due to the high content of H2 (45 vol%) in the feed gas that favours the reverse reactions of NH3 decomposition and H2S adsorption, the increased surface coverage of the active α-Fe phase by adsorbed hydrogen, and the competition of α-Fe for the reverse water-gas shift reaction. Besides, it was discovered that the temperature significantly affected the removal of NH3 and H2S in simulated biomass producer gas and thus it needs to be optimised.

¡@¡@In this thesis, the formation of m-plane (10-10) Gallium nitride (GaN) on the surface of a-plane (100) lithium gallate (LiGaO2, LGO) substrates via nitridation with ammonia (NH3) at high temperature. The parameters in this research were mainly focus on temperature, ammonia flow rate, reaction pressure, and growth time. ¡@¡@Specimens were analyzed with various instruments. X-ray Diffraction patterns showed that the nitridation process on LGO substrate resulted in the formation of the GaN single crystalline films. The crystalline quality of the GaN film could be improved by changing parameters of nitridation process. Scanning electron microscope image showed that the structure of GaN films was nanoporous. A red shift in the E2(high) phonon peak of GaN from micro-Raman indicates a compressive stress in the porous GaN with respect to the single crystalline epitaxial GaN. PL intensity ratio (INBE/IYL) of the porous GaN was found to be increased as changing parameters of nitridation process, namely the optical and crystalline quality of porous GaN was improved. Hall measurement showed that the porous GaN was p-type, and it had high hole concentration, good mobility, and low resistivity. Analyses of the elements depth profile by Auger electron spectroscopy. Transmission electron microscopy was used to observe the high resolution cross-section of porous GaN. From the selected area electron diffraction patterns, the orientation relationship between porous and LGO was determined as [100]LGO//[10-10]GaN and [0-10]LGO//[11-20]GaN when zone axis was [0001].

Submitted by Alexia Morello da Silva Cascaldi null (alexia.morello@yahoo.com.br) on 2017-09-19T05:33:05Z No. of bitstreams: 1 Dissertação_Alexia_Morello_da_Silva_Cascaldi.pdf: 844332 bytes, checksum: 98e363c052f3354ad72b45c70bf2f3bd (MD5) / Approved for entry into archive by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-09-19T20:48:59Z (GMT) No. of bitstreams: 1 cascaldi_ams_me_jabo.pdf: 844332 bytes, checksum: 98e363c052f3354ad72b45c70bf2f3bd (MD5) / Made available in DSpace on 2017-09-19T20:48:59Z (GMT). No. of bitstreams: 1 cascaldi_ams_me_jabo.pdf: 844332 bytes, checksum: 98e363c052f3354ad72b45c70bf2f3bd (MD5) Previous issue date: 2017-07-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O nitrogênio é um nutriente essencial para as culturas, entretanto seu aproveitamento está sujeito a muitas perdas no sistema solo-planta-atmosfera. Alguns compostos têm sido utilizados com o propósito de reduzir essas perdas, aumentando a eficiência dos fertilizantes nitrogenados. O objetivo deste trabalho foi avaliar o efeito da utilização do estabilizante de ureia NZone Max, em relação às perdas por volatilização de amônia (NH3) e lixiviação de nitrato (NO3-), em cultivo de Brachiaria brizantha cv. Marandu, adubada com ureia, sob quatro lâminas de irrigação. Os tratamentos consistiram das lâminas de irrigação correspondentes a 0,20; 0,40; 0,60 e 0,80 da evapotranspiração de referência, com adição ou não de estabilizante de ureia, com aplicação de 100 kg ha-1 de N. O delineamento experimental foi em faixa com parcela subdividida, com lâminas na parcela e estabilizante na subparcela, com 4 repetições. A coleta da amônia volatilizada foi feita com câmaras coletoras instaladas em cada parcela, para posterior quantificação em laboratório. Foram também coletadas amostras da solução do solo para análise química. Os dados foram submetidos à análise de variância pelo teste F e a comparação de médias foi feita pelo teste Tukey (5%). A quantidade de amônia volatilizada foi crescente até o terceiro dia após a adubação, quando atingiu os maiores valores, diminuindo a partir de então, tanto na presença quanto na ausência do estabilizante de ureia, para as 4 lâminas de irrigação. A menor lâmina apresentou a maior quantidade de amônia volatilizada, enquanto que a maior lâmina foi a de menor volatilização. Não houve diferença entre os tratamentos com e sem o uso do estabilizante, tanto para a quantidade de amônia volatilizada, quanto para os valores de nitrato, amônio, N-total, pH e condutividade elétrica da solução do solo. Portanto, a adição do estabilizante NZone Max à ureia não promoveu redução das perdas por volatilização de amônia e lixiviação de nitrato. / Nitrogen is an essential nutrient for crops, however its use is subject to many losses in the soil-plant-atmosphere system. Some compounds have been used for the purpose of reducing these losses, increasing the efficiency of nitrogen fertilizers. The objective of this work was to evaluate the effect of NZone Max urea stabilizer in relation to losses by ammonia (NH3) volatilization and nitrate (NO3-) leaching in a Brachiaria brizantha cv. Marandu crop, fertilized with urea, under four irrigation depths. The treatments consisted of irrigation depths corresponding to 0.20, 0.40, 0.60 and 0.80 of the reference evapotranspiration, with and without urea stabilizer, with application of 100 kg ha-1 of N. The treatments were arranged in a split-plot strip design, with irrigation depths in the plot and stabilizer in the subplot, with 4 replications. The volatilized ammonia was collected with chambers installed in each plot, for subsequent quantification in the laboratory. Soil solution samples were also collected for chemical analysis. The data were submitted to analysis of variance by the F test and the means were compared by the Tukey test (5%). The amount of volatilized ammonia increased until the third day after fertilization, when it reached the highest values, decreasing thereafter, both in the presence and absence of the urea stabilizer, for the 4 irrigation depths. The lower irrigation depth presented a higher amount of volatilized ammonia, while the higher depth was lower volatilization. There was no difference between the treatments with or without stabilizer, for the amount of ammonia volatilized, as well as for the nitrate, ammonium, N-total, pH and electrical conductivity of the soil solution. Thus, the addition of the NZone Max stabilizer to the urea did not promote reduction of the losses by ammonia volatilization and nitrate leaching.

This thesis describes a series of experiments that were undertaken to extend the limits of output power and wavelength coverage of optically pumped mid-infrared lasers. Initially, two new cw Raman lasers operating at wavelengths of 11.5 and 12.5 pm were developed. Maximum output powers of 650 add 150 mW were produced, with pump powers of 11 and 3.3 W, respectively. The effect of the pump offset on the output power was then determined by measuring the efficiency of an NH3 laser pumped at frequency offsets of 94 and 274 MHz. In lasers ope rating in pure NH3 the larger pump offset required a greater pump intensity to reach threshold, but efficiency increased with pump offset. Higher NH3 pressures could be used at larger pump offsets and the improved efficiency was attributed to reduced saturation effects at the higher operating pressures. Experiments carried out with NH3 inversion lasers have greatly increased the output powers available at a large number of wavelengths in the 10 to 14 um range. In a buffered NH3 mixture, the sR(5,0) transition was pumped on resonance. Collisions with either N2 or Ar buffer gases were effective in thermalizing the rotational populations in the v2=1 vibrational level and producing gain on a wide range of frequencies. Output powers as large as 3.5 W on a single Tine and greater than 5 W multi-line were produced, at efficiencies of 20 and 30 % respectively. The number of lasing wavelengths increased substantially, as more than forty ortho-NH3 transitions were observed to lase in a grating-tuned cavity. The optical pumping technique was then used for the first time to produce line-tunable lasing on para-NH3 transitions. The sR(5,1) transition was pumped near resonance and 24 para-transitions were observed to lase. In total, lasing was achieved on 65 different transitions in 14NHg, with wave lengths of 10.3 to 13.8 pm. / Thesis / Master of Science (MS)

As perdas gasosas nitrogenadas são consideráveis em pastagens e a utilização de métodos simples e acessíveis para mensurá-las é de extrema necessidade na avaliação do ciclo de N nesses sistemas. O objetivo desse trabalho foi determinar métodos para quantificar o NH3 volatilizado de fertilizantes nitrogenados aplicados ao solo, que tenham pouca interferência nos processos de volatilização. Foram conduzidos dois experimentos em casa de vegetação pertencente ao Departamento de Zootecnia da Faculdade de Zootecnia e Engenharia de Alimentos. O delineamento experimental utilizado foi inteiramente casualizado com cinco repetições. No primeiro experimento os tratamentos foram: absorvedor de espuma a 1, 10, 20 e 30 cm do solo; absorvedor de papel a 1, 10, 20 e 30 cm do solo; coletor semi-aberto estático; e balanço de 15N (método de referência). E no segundo experimento os tratamentos foram: absorvedor de espuma a 1, 5, 10 e 20 cm do solo; absorvedor de papel a 1, 5, 10 e 20 cm do solo; absorvedor com ácido a 1, 5 e 10 cm do solo; coletor semi-aberto estático; e balanço de 15N (método de referência). Nos dois experimentos quantificou-se o N (NH3) volatilizado. As perdas de N-NH3 determinadas pelo método do balanço de 15N, no experimento 1, foram elevadas (73% do N aplicado) e nenhum dos absorvedores avaliados apresentou volatilização de N-NH3 igual ao balanço de 15N. Isso provavelmente ocorreu devido ao elevado valor de pH do solo e a intensa corrente de ar formada pelos exaustores da casa de vegetação, o que contribuiu para o aumento da volatilização de N-NH3 e prejudicou a sua captação pelos absorvedores. No experimento 2, o coletor semi-aberto, o absorvedor de espuma a 1cm, os absorvedores de papel a 1 e 5 cm e os absorvedores com ácido a 1; 5 e 10 cm apresentaram valores acumulados de N-NH3 volatilizado iguais ao balanço de 15N, estimando portanto as reais perdas acumuladas de N-NH3 (p<0,0001). O absorvedor de espuma a 1 cm foi o que apresentou a curva de perdas de N-NH3 mais semelhante a do coletor semi-aberto, que foi considerado o método de referência para as comparações de perdas de N-NH3 a cada dois dias durante o período experimental. / Gaseous losses are considerable in pastures, therefore the utilization of simple and accessible methods to measure them are extremely necessary to evaluate the cycle of N in these systems. This work aimed to determine methods that quantify volatilized NH3 of nitrogenous fertilizers applied to soil which have little interferente in the volatilization processes. Two experiments in a greenhouse from Departamento de Zootecnia of Faculdade de Zootecnia e Engenharia de Alimentos were conducted. Completely randomized experimental design was used with five repetitions. Treatments from the first experiment were: foam absorber at 1, 10, 20 and 30 cm from the ground; paper absorber at 1, 10, 20 and 30 cm from the ground; static semi-open collector and 15N balance (reference method). In the second experiment the treatments used were as follows: foam absorber at 1, 5, 10 and 20 cm from the ground; paper absorber at 1, 5, 10 and 20 cm from the ground; acid absorber at 1, 5 and 10 cm from the ground; static semi-open collector and 15N balance (reference method). Both experiments quantified volatilized N –NH3. N-NH3 losses determined by 15N balance method in experiment 1 were high (73% of the applied N) and none of the evaluated absorbers presented the same N-NH3 volatilization as the 15N balance. These results probably occurred due to the high pH value from the soil and the intense airflow generated by the greenhouse fans what allowed the increase of N-NH3 volatilization and harmed its capitation by the absorbers. In experiment 2, semi-open collector, foam absorber at 1cm, paper absorbers at 1 and 5 cm and acid absorbers at 1; 5 and 10 cm presented equal accumulated values of volatilized N-NH3 as 15N balance, therefore estimating the real N-NH3 accumulated losses (p<0,0001). Foam absorber at 1cm presented curves of N-NH3 losses similar to semi-open collector, considered the reference method to compare N-NH3 losses on each two days during the experimental period.

As perdas gasosas nitrogenadas são consideráveis em pastagens e a utilização de métodos simples e acessíveis para mensurá-las é de extrema necessidade na avaliação do ciclo de N nesses sistemas. O objetivo desse trabalho foi determinar métodos para quantificar o NH3 volatilizado de fertilizantes nitrogenados aplicados ao solo, que tenham pouca interferência nos processos de volatilização. Foram conduzidos dois experimentos em casa de vegetação pertencente ao Departamento de Zootecnia da Faculdade de Zootecnia e Engenharia de Alimentos. O delineamento experimental utilizado foi inteiramente casualizado com cinco repetições. No primeiro experimento os tratamentos foram: absorvedor de espuma a 1, 10, 20 e 30 cm do solo; absorvedor de papel a 1, 10, 20 e 30 cm do solo; coletor semi-aberto estático; e balanço de 15N (método de referência). E no segundo experimento os tratamentos foram: absorvedor de espuma a 1, 5, 10 e 20 cm do solo; absorvedor de papel a 1, 5, 10 e 20 cm do solo; absorvedor com ácido a 1, 5 e 10 cm do solo; coletor semi-aberto estático; e balanço de 15N (método de referência). Nos dois experimentos quantificou-se o N (NH3) volatilizado. As perdas de N-NH3 determinadas pelo método do balanço de 15N, no experimento 1, foram elevadas (73% do N aplicado) e nenhum dos absorvedores avaliados apresentou volatilização de N-NH3 igual ao balanço de 15N. Isso provavelmente ocorreu devido ao elevado valor de pH do solo e a intensa corrente de ar formada pelos exaustores da casa de vegetação, o que contribuiu para o aumento da volatilização de N-NH3 e prejudicou a sua captação pelos absorvedores. No experimento 2, o coletor semi-aberto, o absorvedor de espuma a 1cm, os absorvedores de papel a 1 e 5 cm e os absorvedores com ácido a 1; 5 e 10 cm apresentaram valores acumulados de N-NH3 volatilizado iguais ao balanço de 15N, estimando portanto as reais perdas acumuladas de N-NH3 (p<0,0001). O absorvedor de espuma a 1 cm foi o que apresentou a curva de perdas de N-NH3 mais semelhante a do coletor semi-aberto, que foi considerado o método de referência para as comparações de perdas de N-NH3 a cada dois dias durante o período experimental. / Gaseous losses are considerable in pastures, therefore the utilization of simple and accessible methods to measure them are extremely necessary to evaluate the cycle of N in these systems. This work aimed to determine methods that quantify volatilized NH3 of nitrogenous fertilizers applied to soil which have little interferente in the volatilization processes. Two experiments in a greenhouse from Departamento de Zootecnia of Faculdade de Zootecnia e Engenharia de Alimentos were conducted. Completely randomized experimental design was used with five repetitions. Treatments from the first experiment were: foam absorber at 1, 10, 20 and 30 cm from the ground; paper absorber at 1, 10, 20 and 30 cm from the ground; static semi-open collector and 15N balance (reference method). In the second experiment the treatments used were as follows: foam absorber at 1, 5, 10 and 20 cm from the ground; paper absorber at 1, 5, 10 and 20 cm from the ground; acid absorber at 1, 5 and 10 cm from the ground; static semi-open collector and 15N balance (reference method). Both experiments quantified volatilized N –NH3. N-NH3 losses determined by 15N balance method in experiment 1 were high (73% of the applied N) and none of the evaluated absorbers presented the same N-NH3 volatilization as the 15N balance. These results probably occurred due to the high pH value from the soil and the intense airflow generated by the greenhouse fans what allowed the increase of N-NH3 volatilization and harmed its capitation by the absorbers. In experiment 2, semi-open collector, foam absorber at 1cm, paper absorbers at 1 and 5 cm and acid absorbers at 1; 5 and 10 cm presented equal accumulated values of volatilized N-NH3 as 15N balance, therefore estimating the real N-NH3 accumulated losses (p<0,0001). Foam absorber at 1cm presented curves of N-NH3 losses similar to semi-open collector, considered the reference method to compare N-NH3 losses on each two days during the experimental period.

This thesis describes a series of experiments that were undertaken to extend the limits of output power and wavelength coverage of optically pumped mid-infrared lasers. Initially, two new CW Raman lasers operating at wavelengths of 11.5 and 12.5 pm were developed. Maximum powers of 650 and 150 mW were produced, with pump powers of 11 and 3.3 W, respectively. The effect of the pump offset on the output power was then determined by measuring the efficiency of an NHg laser pumped at frequency offsets of 94 and 274 MHz. In lasers operating in pure NH3, the larger pump offset required a greater pump intensity to reach threshold, but efficiency increased with pump offset. Higher NH3 pressures could be used at larger pump offsets and the improved efficiency was attributed to reduced saturation effects at the higher operating pressures. Experiments carried out with NHg inversion lasers have greatly increased the output powers available at a large number of wavelengths in the 10 to.14 pm range. In a buffered NH3 mixture, the sR(5,0) transition was pumped on resonance. C^llis;o^r^s with either — or Ar buffer gases were effective in thermalizing the rotational populations in the v>2=1 vibrational level and producing gain on a wide range of frequencies. Output powers as large as 3.5 W on a single line and greater than 5 W multi-line were produced, at efficiencies of 20 and 30 % respectively. The number of lasing wavelengths increased substantially, as more than forty ortho-NH3 transitions were observed to lase in a grating-tuned cavity. The optical pumping technique was then used for the first time to produce line-tunable lasing on para-NH3 transitions. The sR(5,l) transition was pumped near resonance and 24 para-transst'lons were observed to lase. In total, lasing was achieved on 65 different transitions in 14NH3, with wavelengths of 10.3 to 13.8 pm. / Thesis / Master of Science (MSc)

Stickoxide NOx werden von Menschenhand in verschiedenen Verbrennungsprozessen emittiert. Die selektive katalytische Reduktion mit Ammoniak (NH3-SCR) hat sich weltweit als wichtigste Methode zur Minderung von NOx-Emissionen etabliert. Derzeit erhältliche Katalysatoren für die NH3-SCR werden bei Temperaturen unterhalb von 473 K stark in Gegenwart von Wasser desaktiviert, welches unvermeidbar in Abgasen aus der Verbrennung von organischen Stoffen enthalten ist. In dieser Arbeit werden drei verschiedene Arten der Modifikation von SCR-Katalysatoren diskutiert, die eine gesteigerte H2O-Resistenz bewirken. Eine Methode ist die Verwendung von mischoxidischen Trägermaterialien, eine Andere ist eine mischoxidische aktive Komponente und schließlich eine postpräparative Oberflächenmodifikation mit Organosilylgruppen. Die Katalysatoren wurden sowohl auf ihre katalytische Aktivität als auch auf ihre adsorptiven, redox und andren Oberflächeneigenschaften untersucht. Die Wechselwirkungen zwischen H2O und der Katalysatoroberfläche wurden mittels temperaturprogrammierter Desorption (TPD), isothermaler Adsorption bei erhöhtem Druck und einer gravimetrischen Methode untersucht. Besonders die H2O-TPD hat sich als eine leistungsstarke Methode für diesen Zweck herausgestellt. Jede der drei Modifikationen bewirkte eine Verminderung der Wechselwirkungen zwischen H2O und der Katalysatoroberfläche. Neben einer allgemeinen Erhöhung der Aktivität eines SCR-Katalysators, wird die gezielte Verminderung dieser Wechselwirkungen als Schlüsselrolle in der Entwicklung von Katalysatoren mit verbesserter H2O-Resistenz angesehen. Jedoch gibt es zur Zeit kaum Publikationen, die diesen Zusammenhang behandeln. Daneben wurde auch die Bildung von N2O als ungewünschtes Nebenprodukt bei der SCR-Reaktion untersucht. Dessen Treibhauspotential entspricht ungefähr dem 300-fachen von CO2. Die Verwendung von einem mischoxidischem Trägermaterial kann die Freisetzung von N2O während der SCR verringern, was größtenteils auf die Unterdrückung der Bildung nach einem ER-Mechanismus zurückgeführt wurde. Auch die N2O-Bildung wird in vielen Publikationen über die Entwicklung von SCR-Katalysatoren nicht betrachtet.:0.1 Abbreviations 0.2 Symbols 1 Introduction and Objectives 2 Literature Overview 2.1 NH3-SCR 2.1.1 NH3-SCR Catalysts 2.1.2 Mechanisms of NH3-SCR Reaction 2.1.3 N2O-Formation under SCR-Conditions 2.2 Deactivation of NH3-SCR Catalysts 2.2.1 Deactivation by H2O 2.2.2 Deactivation by SO2 2.3 Low-Temperature NH3-SCR 2.3.1 Requirements and Challenges of LT-SCR 2.3.2 LT-SCR Catalysts 2.4 Silylation of Metal Oxide Surfaces 3 Experimental Section 3.1 Catalyst Preparation 3.1.1 Support Modification with Different Metal Oxides 3.1.2 Deposition of Active Component 3.1.3 Catalyst Modification with Organosilyl Groups 3.2 Catalyst Characterization 3.2.1 Texture Analysis 3.2.2 Phase Analysis 3.2.3 Elementary Analysis 3.2.4 Adsorption Properties 3.2.5 Surface Spectroscopy 3.2.6 Redox Properties 3.3 Catalytic Experiments 4 Results and Discussion 4.1 Impact of Mixed-Oxide Support on Catalyst Activity 4.1.1 Impact in Dry Gas-Flow: Reduced N2O-Emission 4.1.1.1 Catalytic Activity 4.1.1.2 Catalyst Characterization 4.1.1.3 Discussion 4.1.2 Impact in Wet Gas-Flow: Higher H2O-Resistance 4.1.2.1 Catalytic Activity 4.1.2.2 Catalyst Characterization 4.1.2.3 Discussion 4.1.3 Summary of SiO2-Impact 4.2 Mn-Ce Mixed-Oxide as Active Component 4.2.1 Catalytic Activity 4.2.2 Catalyst Characterization 4.2.3 Discussion and Summary 4.3 Catalyst Modification with Organosilyl Groups 4.3.1 Stability of Organosilyl Groups 4.3.2 Impact of Organosilyl Modification on H2O-Adsorption 4.3.3 Impact of Organosilyl Modification on Catalytic Activity in Pre- and Absence of H2O 4.3.3.1 Catalytic Activity 4.3.3.2 Catalyst Characterization 4.3.3.3 Discussion 4.3.4 Summary of Organosilyl Modification 4.4 Discussion on the Investigation of H2O-Adsorption 5 Conclusions and Outlook 5.1 Conclusions 5.2 Outlook 6 References 7 Appendix 7.1 Evaluation of H2O-Sorption Data through BET-Theory 7.2 Evaluation of Kinetic SCR Investigation 7.3 Calculation of the Average Oxidation State of Mnz+ from H2-TPR 7.4 Calculation of the Surface-Density of Mn 7.5 Supplementary Data 7.6 Scientific Contributions 7.7 Curriculum Vitae 8 Summary (german) 8.1 Einleitung 8.2 Experimentelles 8.3 Ergebnisse und Diskussion 8.3.1 Einfluss eines mischoxidischen Trägermaterials auf die katalytische Aktivität 8.3.2 Mn-Ce-Mischoxide als aktive Komponente 8.3.3 Modifikation von Katalysatoren mit Organosilyl-Gruppen 8.4 Schlussfolgerungen / Nitrogen oxides NOx were anthropogenically emitted by various combustion processes. The selective catalytic reduction with ammonia (NH3-SCR) has been established worldwide as the most important technique for the abatement of NOx . Currently available catalysts for NH3-SCR become strongly deactivated at temperatures below 473 K in presence of H2O which is unavoidable present in the exhaust gas arising from the combustion of organic matter. In this work three different kinds of a modification of an SCR-catalyst were discussed that cause a higher H2O-resistance. One is the application of a mixed-oxide support material, the other is a mixed-oxide active component and finally a post-preparative surface modification with organosilyl-groups. The catalysts were assessed for their catalytic activity as well as their adsorptive, redox and other surface properties. The interactions between H2O and the catalyst surface were investigated by means of temperature programmed desorption (TPD), isothermal adsorption at elevated pressure and a gravimetric method. Especially the H2O-TPD turned out to be a powerful method for this purpose. Each of the three modifications caused a reduction in the H2O-catalyst interactions. Beside a general increase of the activity of an SCR-catalyst, the purposeful reduction of these interactions is considered to play a key role in the development of catalysts with an enhanced H2O-resistance. However, there is a lack of publications that deal with this correlation. Also the formation of the unwanted by-product N2O was investigated. Its global warming potential is about 300-times that of CO2. The application of a mixed-oxide support can reduce the release of N2O during SCR which was attributed mainly to the suppression of the ER-type formation pathway. Also the N2O-formation is not considered in many publications dealing with the development of SCR-catalysts.:0.1 Abbreviations 0.2 Symbols 1 Introduction and Objectives 2 Literature Overview 2.1 NH3-SCR 2.1.1 NH3-SCR Catalysts 2.1.2 Mechanisms of NH3-SCR Reaction 2.1.3 N2O-Formation under SCR-Conditions 2.2 Deactivation of NH3-SCR Catalysts 2.2.1 Deactivation by H2O 2.2.2 Deactivation by SO2 2.3 Low-Temperature NH3-SCR 2.3.1 Requirements and Challenges of LT-SCR 2.3.2 LT-SCR Catalysts 2.4 Silylation of Metal Oxide Surfaces 3 Experimental Section 3.1 Catalyst Preparation 3.1.1 Support Modification with Different Metal Oxides 3.1.2 Deposition of Active Component 3.1.3 Catalyst Modification with Organosilyl Groups 3.2 Catalyst Characterization 3.2.1 Texture Analysis 3.2.2 Phase Analysis 3.2.3 Elementary Analysis 3.2.4 Adsorption Properties 3.2.5 Surface Spectroscopy 3.2.6 Redox Properties 3.3 Catalytic Experiments 4 Results and Discussion 4.1 Impact of Mixed-Oxide Support on Catalyst Activity 4.1.1 Impact in Dry Gas-Flow: Reduced N2O-Emission 4.1.1.1 Catalytic Activity 4.1.1.2 Catalyst Characterization 4.1.1.3 Discussion 4.1.2 Impact in Wet Gas-Flow: Higher H2O-Resistance 4.1.2.1 Catalytic Activity 4.1.2.2 Catalyst Characterization 4.1.2.3 Discussion 4.1.3 Summary of SiO2-Impact 4.2 Mn-Ce Mixed-Oxide as Active Component 4.2.1 Catalytic Activity 4.2.2 Catalyst Characterization 4.2.3 Discussion and Summary 4.3 Catalyst Modification with Organosilyl Groups 4.3.1 Stability of Organosilyl Groups 4.3.2 Impact of Organosilyl Modification on H2O-Adsorption 4.3.3 Impact of Organosilyl Modification on Catalytic Activity in Pre- and Absence of H2O 4.3.3.1 Catalytic Activity 4.3.3.2 Catalyst Characterization 4.3.3.3 Discussion 4.3.4 Summary of Organosilyl Modification 4.4 Discussion on the Investigation of H2O-Adsorption 5 Conclusions and Outlook 5.1 Conclusions 5.2 Outlook 6 References 7 Appendix 7.1 Evaluation of H2O-Sorption Data through BET-Theory 7.2 Evaluation of Kinetic SCR Investigation 7.3 Calculation of the Average Oxidation State of Mnz+ from H2-TPR 7.4 Calculation of the Surface-Density of Mn 7.5 Supplementary Data 7.6 Scientific Contributions 7.7 Curriculum Vitae 8 Summary (german) 8.1 Einleitung 8.2 Experimentelles 8.3 Ergebnisse und Diskussion 8.3.1 Einfluss eines mischoxidischen Trägermaterials auf die katalytische Aktivität 8.3.2 Mn-Ce-Mischoxide als aktive Komponente 8.3.3 Modifikation von Katalysatoren mit Organosilyl-Gruppen 8.4 Schlussfolgerungen

<p> An experimental study of vibrational energy transfer in ortho and para NH3(v2) is presented. The vibrational relaxation rates are necessary to characterize mid-IR pulsed and cw NH3 lasers, and the interpretation of these rates is of theoretical importance. Accurate information on the (V-T) process in NH3/N2 mixtures and the (V-V) energy transfer between ortho and para 15NH3 and 14NH3 is now available. </p> <p> First, NH 3 linestrengths and linewidths were accurately measured with a tunable diode laser (TDL) so that ammonia concentrations could be calculated from TDL scans. The energy transfer mechanisms were studied by exciting the v2 vibration of NH3 with a Q-switched cO2 laser and probing the subsequent changes in population with a TDL. A difference in v 2 lifetimes was observed between ortho and para NH3 transitions, and is explained by a (V-V) transfer of energy between the NH3 species. An isolated ortho 15NH3 absorption line was pumped and vibrational transfer of energy was observed to ortho and para 14NH3 and 15NH3. </p> / Thesis / Master of Science (MSc)

Na busca de alternativas para mensurar a emissão foliar de amônia (NH3) e minimizar as perdas de N-NH3 em pastagens, foram realizados três trabalhos. Os dois primeiros com objetivo de verificar se o absorvedor com espuma, já utilizado na quantificação da volatilização de N-NH3, também é eficiente para mensurar a emissão foliar, sem causar alterações no processo de perda de nitrogênio. O terceiro trabalho, realizado em pastagem de capim Colonião (Panicum maximum Jacq. cv. Colonião) no verão, inverno e primavera, avaliou o efeito da aplicação de lâminas de água, após a adubação com uréia, sobre as perdas de N-NH3 do solo por volatilização e emissão foliar. O absorvedor de amônia com espuma não causa alteração no processo de perda de N-NH3 e colocado 1 cm acima das folhas superiores, é efetivo em capturar o N-NH3 perdido por emissão foliar da pastagem, quando se fertiliza em superfície com nitrato de amônio e uréia. A aplicação de água imediatamente após a adubação com uréia é eficiente para reduzir as perdas de NNH3 por volatilização. No verão, a aplicação de 3,2 mm de água foi suficiente para reduzir as perdas de N-NH3 para menos de 3,1 % do N aplicado, enquanto na ausência de irrigação ocorreram perdas de 30,5%. A taxa de volatilização é influenciada pela quantidade de água disponível no solo, sendo baixa quando a uréia é aplicada em solo seco ou quando o solo seca rapidamente, mesmo que a temperatura ambiente seja elevada. A emissão foliar de N-NH3 não foi influenciada pela aplicação ou não de água, após a adubação com uréia. / In search of alternatives to measure ammonia (NH3) foliar emission and minimize N-NH3 losses in pasture three research works were accomplished. The two first works aimed at checking whether or not the foam absorber, which was already used to quantify N-NH3 volatilization, is also efficient to measure foliar emission without interfering in nitrogen loss process. The third one was performed in Panicum maximum Jacq. cv. Colonião pasture during three different seasons and evaluated the use of irrigation levels after urea fertilization on N-NH3 losses through volatilization and foliar emission. The ammonia foam absorber does not alter N-NH3 loss process and when place at height of 1 cm from the upper leaves it is effective in capturing N-NH3 lost through foliar emission when fertilization is done superficially with ammonium nitrate and urea. Water application immediately after fertilization is efficient to reduce N-NH3 losses through volatilization. During summer the use of 3.2 mm water was enough to decrease N-NH3 loss to less than 3.1% of applied N, while the lack of irrigation caused 30.5% losses. Volatilization rate is influenced by the quantity of water available in the soil, being low when urea is applied to dry soil or when the soil dries fast even if the environment temperature is high. N-NH3 foliar emission was not influenced by water application after urea fertilization.