The purpose of this investigation was to determine the effects of mild pressures and hydrogen concentrations on the formation of ammonia by slow neutron irradiation of gaseous hydrogen-nitrogen systems. A secondary purpose of this investigation was to determine the effects of neutron irradiation on ammonia synthesis. Apparatus consisted of two parallel reaction tubes identical except that one was under an average neutron flux of 700 neutrons per square centimeter-second in a paraffin howitzer. The reaction tubes were of pyrex with inside diameter of two inches and length of four feet. Ammonia produced was absorbed in ten-milliliter portions of very dilute hydrochloric acid, and the rinsings from the tube walls were added to the sample. Analyses of the samples were made with Nessler’s reagent and a colorimeter. Tests were performed at pressures of 3.0, 4.0, and 5.0 atmospheres and at hydrogen-nitrogen molar ratios of 3.0 and 6.0. Reaction time was 24 hours, and average total flux was 6.05 x 10⁷ neutrons per square centimeter. It was found that the amount of ammonia formed in the irradiated reaction tube was from 4 percent to 73 percent greater than the amount formed without irradiation, the results for testing the effects of ratio of reactants and of pressure were too scattered to permit any valid conclusions, and that ammonia synthesis under neutron irradiation is worthy of further study as a possible industrial process. / Master of Science

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24628号 / 工博第5134号 / 新制||工||1981(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 陰山 洋, 教授 阿部 竜, 教授 藤原 哲晶 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Novel ceramic membrane cells of BaCe₀.₅Zr₀.₃Y₀.₁₆Zn₀.₀₄O[subscript(3-δ)] (BCZYZ), a proton-conducting oxide, have been developed for electrocatalytic ammonia synthesis. Unlike the industrial Haber-Bosch process, in this work an attempt to synthesise ammonia at atmospheric pressure has been made. The membrane cell fabricated by tape casting and solution impregnation comprises of a 200 μm-thick BCZYZ electrolyte and impregnated electrode composites. Electrocatalysts for anode and cathode were investigated. For the anode, the co-impregnation of Ni and CeO₂ provided excellent electrode performance including high catalytic activity, sintering stability and compatibility with the BCZYZ electrolyte. The best composition was the mixture of 25 wt% NiO and 10 wt% CeO₂. A symmetrical cell prepared with this electrode composition revealed low polarisation resistances of 1.0 and 0.45 Ωcm² in humidified 5% H₂/Ar at 400 and 500 °C, respectively. For the cathode, 25 wt% of impregnated Fe oxide provided a satisfactory performance in non-humidified N₂ atmosphere. Significant amounts of ammonia were produced from the single cell with Ni-CeO₂ anode and Fe oxide cathode at 400-500 °C under atmospheric pressure. Ammonia formation rate was enhanced by Pd catalyst addition and electrochemical performance was improved by Ru addition. The highest ammonia formation rate of 4 x 10⁻⁹ mols⁻¹cm⁻² was attained using the cell with a Pd-modified Fe cathode at 450 °C. The formation reaction of ammonia typically consumed around 1-2.5 % of total applied current while most of the applied current was employed in H⁺ reduction. The total current efficiency of around 90-100 % could be obtained from the membrane cells.

Ru/C type ammonia synthesis catalysts are known to be poisoned by hydrogen. In order to elucidate a mechanism for hydrogen poisoning, H2 adsorption and spillover on Ru based ammonia synthesis catalysts were investigated. Supported Ru catalysts and Na promoted Ru catalyst were prepared by incipient wetness impregnation of Ru(NO)(NO3)3 on SiO2, SBA-15, CNT and Vulcan supports. Dispersion value of the catalysts was determined via H2 chemisorption and Transmission Electron Microscopy (TEM) characterization techniques. Over SBA-15 support, the dispersion of the catalyst determined by two different characterization techniques were in agreement. On the other hand, over CNT and SiO2 supports dispersion measured by TEM characterization method was higher than H2 chemisorption method. H2 chemisorption measurements performed over extended periods of time were used to determine the spilled over hydrogen amounts over Ru/Vulcan and Na-Ru/Vulcan catalysts at 375 torr and 10 torr H2 pressure at room temperature. By using H2 uptake data measured for extended periods of 6 &ndash / 24 hours, diffusion coefficient of hydrogen species over Vulcan support was calculated assuming a point source diffusion mechanism. Coefficient of diffusion for Ru/Vulcan and Na-Ru/Vulcan was found as 1.39 x 10-14 cm2/sec and 1.23 x 10-14 cm2/sec, respectively at 375 torr. Similarly, at 10 torr, diffusion coefficients of Ru/Vulcan and Na-Ru/Vulcan catalysts were determined as 1.51 x 10-15 cm2/sec and 1.81 x 10-15 cm2/sec, respectively.

The purpose of this thesis was to carry out the experimental study of direct ammonia fuel cells. The use of hydrogen in fuel cells poses a lot of problems. There is a lot of safety, technical and economic issues to be overcome to make its use as a fuel widespread. Ammonia is being considered as a very promising source of hydrogen for fuel cells. However, until now its use in fuel cells has received very little attention. Ammonia presents many advantages over hydrogen and other potential sources of hydrogen such as an easy storage and a world-wide distribution network. Ammonia is a suitable hydrogen carrier and can be easily cracked at high temperatures such as those used in solid oxide fuel cells. The present study was conducting using ammonia as fuel and argon as carrier gas in different solid oxide fuel cell systems: an annular design, a planar design and a micro laminated reactor. The electrolyte materials were calcia stabilized zirconia and yttria stabilized zirconia. As far as the electrodes are concerned, silver, platinum and nickel cermet were used as anode/materials and silver was employed as cathode material. The cell yoltage was measured as function of reactor configuration, space time, ammonia flow rate and ammonia concentration. The results demonstrate the high potential of ammonia over hydrogen when nickel is used as anode material. Solid proton conducting fuel cells operating on ammonia fuel were also studied. The electrolyte materials were fabricated from neodymium and gadolinium doped barium and strontium cerates. The dopant fraction ranged from 1 to 20 wt%. Silver was employed as cathode and anode material and was spray deposited. The application of proton conducting electrolytes results in higher current densities for a given voltage than the using typical oxide ion conductors such as 8mol % yttria stabilized zirconia. The potential of the proton conducting materials for application in ammonia synthesis at atmospheric pressure was also studied. They demonstrated promising results and could prove to be an alternative to the common ammonia synthesis processes.

No description available.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21271号 / 工博第4499号 / 新制||工||1700(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 陰山 洋, 教授 江口 浩一, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

<p> Promoted and supported catalysts were studied with an electron probe microanalyzer. Investigations we re made on promoted fused iron ammonia synthesis catalysts regardirlg the general morphology of the catalysts, the distribution of promoters, and the reduction and poisoning processes . The effect of the promoters on the reduction process , the effect of the impurity silica on the promoter distributions and the nature of the poisoning are discussed. Supported catalysts were prepared by impregnating porous y-alumina spheres with solutions of chromium and/or copper compounds. Concentration profiles for chromium and/or copper , i.e., concentration as a function of distance from the center, were determined on sectioned spheres. Different distributions of these elements on the alumina support were obtained by varying the chemical used, the concentration and the amount of the solution impregnated. Explanations are given for the physical and chemical processes involved during the impregnation . The amount of chromium or copper impregnated is compared with the amount present in each particle. </p> / Thesis / Doctor of Philosophy (PhD)

京都大学 / 新制・論文博士 / 博士(工学) / 乙第13457号 / 論工博第4197号 / 新制||工||1770(附属図書館) / (主査)教授 陰山 洋, 教授 安部 武志, 教授 江口 浩一 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

[pt] O processo industrial para a síntese de amônia utiliza um catalisador de ferro triplamente promovido, operando em condições drásticas a temperaturas entre 400 e 700°C e a uma pressão bastante elevada (aproximadamente 300 atm). Novos catalisadores vêm sendo estudados, em substituição ao ferro, para aumentar ainda mais a produção de NH3. A principal vantagem dos catalisadores a base de rutênio é que eles são menos sensíveis à contaminação pela amônia que os catalisadores a base de ferro. O objetivo deste trabalho foi avaliar catalisadores de rutênio suportados em zeólitas e hidrotalcita promovidos por cátions básicos para a síntese de amônia. Foi verificada a influência do tipo de suporte nos catalisadores de rutênio, do tipo e forma de introdução dos precursores de rutênio, o papel da adição de cátions promotores (Ba e Cs) sobre a interação metal-suporte e na atividade dos catalisadores de rutênio na reação de síntese de amônia. Os catalisadores de rutênio suportados na hidrotalcita apresentaram as maiores conversões na reação de síntese de amônia. Eles apresentaram os mais altos níveis de dispersão e redução das partículas metálicas. O bário, apesar de ter diminuído menos a interação do rutênio com o suporte, se mostrou um promotor mais efetivo na reação de síntese de amônia que o césio. A ordem de introdução do bário apresentou efeitos diferentes, dependendo do suporte, sobre o desempenho dos catalisadores de rutênio. O método de impregnação com carbonila de rutênio se mostrou o mais efetivo, conduzindo a catalisadores de rutênio mais básicos e mais ativos na reação de síntese de amônia. / [en] The industrial ammonia synthesis process uses a triple promoted iron catalyst, operating at drastic temperature conditions between 673K and 973K, and high pressure (300atm). New catalysts have been studied, replacing iron, to increase NH3 production. The main advantage of Ru-based catalysts is that they are less sensitive to poisoning by ammonia than Fe-based catalysts. The aim of this work was to evaluate ruthenium catalysts supported on zeolites and hydrotalcite promoted by basic cations for ammonia synthesis reaction. The influence of the support type on the ruthenium catalysts and of introduction way of the ruthenium precursors was verified. Also the hole of the cationic promoters (Ba and Cs) on the metal-support interaction and on the ruthenium catalysts activity in the ammonia synthesis reaction was examined. The ruthenium catalysts supported on hydrotalcite had the highest conversion in the ammonia synthesis reaction. They presented the highest degrees of dispersion and reduction of metallic particles. The barium, despite having decreased the interaction between the ruthenium and the support, showed to be a more effective promoter on the synthesis of ammonia than the cesium. The barium introduction order resulted in different effects over the ruthenium catalysts performance depending on the support. The impregnation method with ruthenium carbonil was the most effective, leading to more basic ruthenium catalysts and more actives in the ammonia synthesis reaction.