ABSRACT This study was to investigate the removal efficiency and kinetics in oxidation of ammonia solutions (NH3-N) in ranging from 400 mg/L to 1000 mg/L by adding Cu/La/Ce catalyst in process of Wet Air Oxidation (denoted by WAO). All experiments were conducted in semi-batch and continuous reactors in series. The major parameters included temperature, pressure, concentration and pH. In the semi-batch type of WAO experiments, the major parameters were performed at the following conditions: an initial concentration NH3-N of 400 mg/L, temperatures ranging from 423 K to 503 K, a total pressure of 4.0 Mpa, and a pH of 12.0. A removal efficiency of 32.7%was obtained in WAO process at 503 K for180 min, but it could be significantly promote to 95.1% after adding a catalyst of molar ratio 7:2:1.The kinetics of WAO with this catalyst in oxidation of NH3-N solutions, using a test of half-life, was developed nearly to a zero order. The reaction constants were 10.12 KJ/mol, 9.12 KJ/mol, and 6.57 KJ/mol at 503 K, 473 K and 423 K. In the continuous type of WAO experiments, the major parameters were performed at the following conditions: an initial concentration NH3-N of 400 mg/L, a temperature of 503 K, a total pressure of 2.0 Mpa, a pH of 12.0 and a liquid space velocity of 4.5 hr-1 (averagelyresidence time 14 min) . A removal efficiency of NH3-N of 6.5 % only was achieved in WAO process for a space velocity of 4.5 hr-1 (averagely residence time 14 min) , but after adding a catalyst of molar ratio 7:2:1 it increased to 72.3 % for a same residence time and a better efficiency of above 91 % was found for 1.5 hr-1 (averagely residence time 40 min) . For increasing the initial concentration of NH3-N into 600 mg/L, 800 mg/L, and 1000 mg/L the removal efficiency of NH3-N decreased with 85 %,75 % and 69 % for 1.5 hr-1 . Thus, the initial concentration of NH3-N in influent inhibits the removal efficiency in the oxidation process. The higher initial concentration the lower removal efficiency.

The reaction mechanism for the Selective Catalytic Reduction (SCR) of NO by NH3 on V2O5 surface was simulated by means of density functional theory (DFT) calculations performed at B3LYP/6-31G** level. As the initiation reaction, ammonia activation on V2O5 was investigated. Coordinate driving calculations showed that ammonia is adsorbed on Br&oslash / nsted acidic V-OH site as NH4 + species by a nonactivated process with a relative energy of -23.6kcal/mol. Vibration frequencies were calculated as 1421, 1650, 2857 and 2900cm-1 for the optimized geometry, in agreement with the experimental literature. Transition state with a relative energy of -17.1kcal/mol was also obtained. At the end of the Lewis acidic ammonia interaction calculations, it was observed that ammonia is hardly adsorbed on the surface. Therefore, it is concluded that the SCR reaction is initiated more favorably by the Br&oslash / nsted acidic ammonia adsorption. As the second step of the SCR reaction, NO interaction with the preadsorbed NH4 + species was investigated. Accordingly, NO interaction results in the formation of gas phase NH2NO molecule with a relative energy difference of 6.4kcal/mol. For the rest of the reaction sequence, gas phase decomposition of NH2NO was considered. Firstly, one of the hydrogen atoms of NH2NO migrates to oxygen. It then isomerizes in the second step. After that, the reaction proceeds with the isomerization of the other hydrogen. Finally, a second hydrogen atom migration to the oxygen leads to the formation of N2 and H2O. Total relative energy for this reaction series was obtained as -60.12kcal/mol, in agreement with the literature.

QUARESMA, Fabrízia da Silva. Concentração letal média (CL50-96h) e efeitos subletais da amônia não ionizada sobre parâmetros hematológicos de alevinos de tambacu (Colossoma macropomum fêmea x Piaractus mesopotamicus macho). 2016. 53 f. : Dissertação (mestrado) - Universidade Federal do Ceara, Centro de Ciências Agrárias, Departamento de Engenharia de Pesca, Fortaleza-CE, 2016 / Submitted by Nádja Goes (nmoraissoares@gmail.com) on 2016-07-22T14:52:37Z No. of bitstreams: 1 2016_dis_fsquaresma.pdf: 1262731 bytes, checksum: 837440ddfa1a47f8014fdf9a4a826ce7 (MD5) / Approved for entry into archive by Nádja Goes (nmoraissoares@gmail.com) on 2016-07-22T14:52:53Z (GMT) No. of bitstreams: 1 2016_dis_fsquaresma.pdf: 1262731 bytes, checksum: 837440ddfa1a47f8014fdf9a4a826ce7 (MD5) / Made available in DSpace on 2016-07-22T14:52:53Z (GMT). No. of bitstreams: 1 2016_dis_fsquaresma.pdf: 1262731 bytes, checksum: 837440ddfa1a47f8014fdf9a4a826ce7 (MD5) Previous issue date: 2016 / Ammonia is a toxic compound to aquatic organisms and at high concentrations in the water can cause various changes in the animal. Therefore, it becomes important to determine the tolerance of farmed aquatic animals for that substance. Thus, the aim of this study was to determine the median lethal concentration (LC50-96h) of un-ionized ammonia (NH3) in fingerlings tambacu (Colossoma macropomum x Piaractus mesopotamicus) in acute toxicity test and evaluate the effects of concentrations sublethal through the analysis of hematological parameters. In the acute toxicity test, the fingerl ings were exposed to ammonia at concentrations of: 0,09 (control); 0,54; 1,23; 2,52; 3 ,44 and 3,66 mg L-1NH3, which were obtained from the application of NH4Cl. The test lasted 96 hours and mortalities were recorded over that period. The LC50 was determin ed by statistical method Trimmed Spearman Karber . In sublethal exposure to ammonia test concentrations used were : 0,04 (control), 0,19 and 0,35mg L-1NH3.For analysis of hematological parameters, blood samples were collected before the addition of NH4Cl(timezero) and after 96 hours of exposure.The hematological parameters analyzed were: hematocrit ( Ht), hemoglobin(Hb), red blood cell count(RBC) mean corpuscular volume (MCV), mean corpuscular hemoglobin (MCH) and mean corpuscular hemoglobin concentration(MCHC). Data hematological parameters were subjected to analysis of variance (ANOVA) and when there was a significant difference between treatments , the averages were compared in pairs through the Tukey's HSD test (α=0,05).LC50-96h of theun - ionized ammonia (NH3) to fingerlings the hybrid tambacu was 1,63m g L-1. After 96h exposure to 0,35 mg L-1NH3, fish showed significant reductions in hematocrit and the MCV and significant increase in MCHC. Already Hb,RBC and MCH did not differ significantly between treatments and time 0. The exposure to fingerlins tambacu for short period to 0,19 mg L -1 of un-ionized ammonia (NH3) does not cause significant changes in hematological parameters of these fish. / A amônia é um composto tóxico para os organismos aquáticos e em elevadas concentrações na água pode causar diversas alterações no animal. Dessa forma, torna-se importante determinar o limite de tolerância dos animais aquáticos cultivados à essa substância. Sendo assim, o objetivo do trabalho foi determinar a concentração letal média (CL50-96h) da amônia não ionizada (NH3) em alevinos de tambacu (Colossoma macropomum x Piaractus mesopotamicus), em teste de toxicidade aguda e avaliar os efeitos de concentrações subletais através da análise de parâmetros hematólogicos. No teste de toxicidade aguda, os alevinos foram expostos à amônia, nas concentrações de: 0,09 (controle); 0,54; 1,23; 2,52; 3,44 e 3,66 mg L-1 NH3, que foram obtidas a partir da aplicação de NH4Cl. O teste teve duração de 96h e as mortalidades foram registradas ao longo desse período. A CL50 foi determinada pelo método estatístico Trimmed Spearman Karber. No teste de exposição subletal à amônia, utilizou-se as concentrações: 0,04 (controle), 0,19 e 0,35 mg L-1 NH3. Para análise dos parâmetros hematológicos, foram realizadas coletas de sangue antes da adição de NH4Cl (tempo zero) e após 96h de exposição. Os parâmetros hematológicos analisados foram: hematócrito (Ht), taxa de hemoglobina (Hb), número de eritrócitos (RBC), volume corpuscular médio (VCM), hemoglobina corpuscular média (HCM) e concentração de hemoglobina corpuscular média (CHCM). Os dados dos parâmetros hematológicos foram submetidos à análise de variância (ANOVA) e quando houve diferença significativa entre os tratamentos, as médias foram comparadas duas a duas através do teste de Tukey (α=0,05). A CL50-96h da amônia não ionizada (NH3) para alevinos do híbrido tambacu foi 1,63 mg L-1. Após exposição de 96h a 0,35 mg L-1 NH3, os peixes apresentaram reduções significativas no Ht e VCM e aumento significativo na CHCM. Já Hb, RBC e HCM não diferiram significativamente entre os tratamentos e o tempo 0. A exposição de alevinos de tambacu por curto período de tempo a 0,19 mg L-1 de amônia não ionizada (NH3) não causa alterações significativas nos parâmetros hematológicos desses peixes.

CARNEIRO, Hilton Alexandre Vidal. Determinação do consumo, digestões totais, balanço dos compostos nitrogenados e variáveis ruminais em ovinos santa inês alimentados com diferentes níveis de concentrado. 2011. 40 f. Dissertação (Mestrado em zootecnia)- Universidade Federal do Ceará, Fortaleza-CE, 2011. / Submitted by Elineudson Ribeiro (elineudsonr@gmail.com) on 2016-05-17T17:22:03Z No. of bitstreams: 1 2011_dis_havcarneiro.pdf: 331878 bytes, checksum: 37f61126c663af9f49fb518ae1dbaa1e (MD5) / Approved for entry into archive by José Jairo Viana de Sousa (jairo@ufc.br) on 2016-05-27T19:58:55Z (GMT) No. of bitstreams: 1 2011_dis_havcarneiro.pdf: 331878 bytes, checksum: 37f61126c663af9f49fb518ae1dbaa1e (MD5) / Made available in DSpace on 2016-05-27T19:58:55Z (GMT). No. of bitstreams: 1 2011_dis_havcarneiro.pdf: 331878 bytes, checksum: 37f61126c663af9f49fb518ae1dbaa1e (MD5) Previous issue date: 2011 / The experiment w as conducted at the Department of Animal Scie nce, Federal University of Cear a in order to evaluate the effect of four levels of concentr ate (25.0, 37.5, 50.0, 62.5 on DM basis) in the diet of sheep on intake, digestibility of total dry matter (DM), organic matter (OM), crude protein (CP), ether extract (EE), neutral detergent fiber (NDF), neutral detergent fiber corrected for ash and protein (NDF), acid detergent fiber (ADF), total carbohydrates (TC) and non - fiber carbohydrates (NFC ) rumen pH, rumen ammoni a concentrations (NAR), nitrogenous compounds (BN) and plasma urea nitrogen (PUN) . We used sixteen castrated male sheep of Santa Ines body weight of 26.4 kg ± 4.13 kg and approximately seven months old. The animals were housed in individual metabolic cages equipped with collectors and tabs of feces and urine, and mangers for the supply of food and water fountains with water continuously available. The experimental design was randomized blocks with four treatments and four replications, totaling 16 experimen tal plots. T he experimental period lasted 28 days with 21 days of adaptation and seven days to collect samples. The animals were fed diets containing Tifton 85 hay and concentrate (25.0, 37.5, 50.0 and 62.5% ), which consisted of four experimental treatment s. The diets were formulated according to NRC (2007) to meet the nutritiona l requirements of sheep 200g. day - 1 gain. Diets were fed to animals once a day (800h), in form of a total mixture. Daily consumption of dry matter was determined by the difference be tween the bid and the remains of food offered. Feed samples, orts and feces were daily weighed and sampled for chemical analysis subseqente. Feces were collected for seven consecutive days to estimate the digestibility of dietary nutrients. The DM, OM, TC and NDT in g /d were not affected (P> 0.05) by concentrate feed. Increasing linear behavior was observed for intakes of CP, and NFC. For the intake of NDF, NDF, ADF and these linearly decreased. For consumption expressed as% of BW, there was a linear increasing and decreasing for MS to NDF equal behavior was observed for DM intake expressed in (g / kg 0, 75 ). The digestibility 9 of DM, OM, CP, CT and NSC increased (P <0.05) with the level of dietary concentrate. Rumen pH showed a linear response for diets with lower levels of concentrate and a quadratic for the experimental treatment with high level of concentrate as a function of time post - prandial. The diet influenced the concentrations of NH3 - N in the rumen (NAR) decreased linearly to levels of 37.5 and 50% of the concentrate and a quadratic for the 62.5% level of inclusion of dietary concentrate. The concentrate levels did not influence the excretion of nitrogen (N) in faeces ( g /d ) and urine (g /d ). The NB was positive at all levels of concentrate . PUN values among diets, showing a quadratic behavior. The addition of dietary concentrate influences the consumption and digestibility of nutrients, ruminal and promotes retention of nitrogen in the animal's body. / O experimento foi realizado no Departamento de Zootecnia da Universidade Federal do Ceará com o objetivo de avaliar o efeito de quatro níveis de concentrado (25,0; 37,5; 50,0; 62,5 com base na MS) na ração de ovinos, sobre o consumo; as digestibilidades aparentes de matéria seca (MS), matéria orgânica (MO), proteína bruta (PB), extrato etéreo (EE), fibra em detergente neutro (FDN), fibra em detergente neutro corrigida para cinzas e proteína (FDNcp), fibra em detergente ácido (FDA), carboidratos totais (CT) e carboidratos não-fibrosos (CNF); pH ruminal; as concentrações amônia ruminal (NAR), balanço de compostos nitrogenados (BN) e nitrogênio ureico plasmático (NUP) Foram utilizados dezesseis ovinos machos, não castrados, da raça Santa Inês, com peso corporal de 26,4kg ± 4,13kg e aproximadamente sete meses de idade. Os animais foram alojados em gaiolas metabólicas individuais, equipadas com coletores e separadores de fezes e urina, bem como cochos para alimento e bebedouros com água permanentemente à disposição. O delineamento experimental utilizado foi em blocos casualizados com quatro tratamentos e quatro repetições, totalizando 16 parcelas experimentais. O período experimental teve duração de 28 dias, com 21 dias de adaptação e sete dias para coleta de dados. Os animais foram alimentados com rações contendo feno de Tifton 85 e concentrado (25,0; 37,5; 50,0 e 62,5%). As rações foram formuladas conforme o NRC (2007) para atenderem aos requisitos nutricionais de ovinos para ganho de 200 g/dia. As rações foram fornecidas aos animais uma vez ao dia (800h) em forma de mistura total. O consumo de matéria seca foi determinado pela diferença entre o oferecido e as sobras da ração ofertada. Amostras dos alimentos, sobras e fezes foram diariamente pesadas e amostradas para subseqente análises químicas. As fezes foram coletadas durante sete dias consecutivos para estimar a digestibilidade dos nutrientes. Os consumos de MS, MO, CT e NDT expressos em g/dia não foram influenciados pelos níveis de concentrado da ração (P>0,05). Comportamento linear crescente foi verificado para os consumos de PB, EE e CNF. Os consumos de FDN, FDNcp e FDA apresentaram comportamento linear decrescente. Para consumo expresso em %PV, registrou-se comportamento linear crescente para MS e decrescente para FDN, comportamento igual foi verificado para o consumo de MS expresso em (g/kg0,75). Os coeficientes de digestibilidade de MS, MO, PB, EE, CT e CNF aumentaram (P<0,05) com o nível de concentrado na ração. O pH ruminal apresentou comportamento linear para as rações com menores níveis de concentrado e comportamento quadrático para o tratamento experimental com maior nível de concentrado em função do tempo pós-prandial. As dietas experimentais influenciaram as concentrações de N-NH3 no rúmen (NAR) apresentando comportamento linear decrescente para os níveis de 37,5 e 50,0% de inclusão de concentrado e comportamento quadrático para o nível de inclusão 62,5% de concentrado nas rações. Os níveis de concentrado não influenciaram excreção de Nitrogênio (N) nas fezes (g/d) e na urina (g/d). O BN foi positivo em todos os níveis de concentrado. Os valores de NUP diferiram entre as rações, apresentando comportamento quadrático. A adição de concentrado nas rações influencia o consumo e a digestibilidade dos nutrientes, os parâmetros ruminais e promove maior retenção de compostos nitrogenados no corpo do animal.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-04-07T15:02:11Z No. of bitstreams: 1 Marina Menezes de Brito.pdf: 2230882 bytes, checksum: 6d6eefed0cd352899889aef8831943e1 (MD5) / Approved for entry into archive by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-05-09T18:16:19Z (GMT) No. of bitstreams: 1 Marina Menezes de Brito.pdf: 2230882 bytes, checksum: 6d6eefed0cd352899889aef8831943e1 (MD5) / Made available in DSpace on 2016-05-09T18:16:19Z (GMT). No. of bitstreams: 1 Marina Menezes de Brito.pdf: 2230882 bytes, checksum: 6d6eefed0cd352899889aef8831943e1 (MD5) / O óxido nítrico (NO) representa cerca de 95% de todo NOx lançado na atmosfera. Estes são emitidos tanto por fontes móveis quanto por fontes estacionárias, causando problemas ambientais como chuva ácida, smog fotoquímico e depleção na camada de ozônio, o que torna a regulamentação dessas emissões cada vez mais rigorosa. Dentre as principais tecnologias para remoção dos NOx de fontes estacionárias, o tratamento pós combustão é o mais aplicado. Este pode ser feito a partir de reações de redução a nitrogênio (N2), usando gases como amônia (NH3), monóxido de carbono (CO) e hidrocarbonetos, ou de reações de oxidação a NO2 seguida de absorção. Em destaque, a redução com NH3 se mostra mais interessante, pois os produtos de reação são N2 e H2O. Neste trabalho, a redução seletiva não catalítica foi avaliada e indicou que a reação só ocorre em temperaturas acima de 600°C, justificando o uso de catalisadores em temperaturas mais baixas. Testes preliminares indicaram atividade catalítica para óxidos mistos de ferro e titânio na faixa de temperatura de 250-500°C, mas o mesmo não foi observado para os óxidos dos metais puros TiO2 e Fe2O3. Esses materiais foram comparados com o catalisador de composição semelhante ao catalisador padrão da reação (V2O5/TiO2). Com o objetivo de investigar a sinergia dos metais ferro e titânio na reação de SCR- NH3 foram preparados diferentes materiais variando razão Fe/Ti, método de síntese e precursor do titânio. A análise química das amostras mostrou pequenas diferenças na razão Fe/Ti sugerindo pequena perda de precursor de titânio e para a amostra preparada a partir de TiOSO4, foi observado enxofre residual. Os difratogramas de raios-X indicaram a formação de três fases (Fe2O3, TiO2 e Fe2TiO5) para todas as amostras. O refinamento Rietveld indicou a composição de cada fase em cada amostra. Os parâmetros de cela sofreram distorções e sugeriram substituição isomórfica de ambos os metais na estrutura do rutilo (TiO2) e da hematita (Fe2O3). As micrografias das amostras mostraram um aglomerado de partículas distintas e, a formação de poros para as amostras preparadas por combustão. A análise textural mostrou materiais com diferentes texturas e áreas superficiais na faixa de 19 a 120 m² g-1. A dessorção termoprogramada de amônia mostrou que todos os materiais adsorvem amônia, uma etapa do mecanismo da reação de SCR-NH3. Todos os materiais preparados se mostraram ativos na reação de SCR-NH3 chegando a rendimento de 100% a 500°C. Testes de estabilidade foram feitos com duas das amostras em temperaturas de 350 e 450°C e ambos os materiais se mostraram estáveis, mantendo ou aumentando o rendimento a N2. O estudo do mecanismo de reação feito por DRIFT mostrou que há maior formação de bandas relativas a adsorção de NH3 que à adsorção de NO e, portanto, o mecanismo Eley-Rideal é mais consistente para estes materiais. Este estudo ainda supõe que a presença do O2 facilita a adsorção da NH3. O catalisador preparado com TiOSO4 não desativa completamente na presença de SO2. / Nitric oxide (NO) is about 95% of all NOx released into the atmosphere. These are issued by both mobile sources and for stationary sources, causing environmental problems such as acid rain, photochemical smog and depletion in the ozone layer, which makes the regulation of these increasingly stringent emissions. Among the key technologies for the removal of NOx from stationary sources, the post combustion treatment is the most applied. This can be done from the reduction reactions of nitrogen (N2) using gases such as ammonia (NH3), carbon monoxide (CO) and hydrocarbons or oxidation reactions to NO2 followed by absorption. Featured, reduction with NH3 appears more interesting because the reaction products are N2 and H2O. In this work, the selective non-catalytic reduction was measured and indicated that the reaction only occurs at temperatures above 600 ° C, justifying the use of catalysts at lower temperatures. Preliminary tests indicated catalytic activity for mixed iron oxides and titanium in the 250-500 ° C temperature range, but the same was not observed for the oxides of metals pure TiO2 and Fe2O3. These materials were compared with the catalyst composition similar to the standard reaction catalyst (V2O5 / TiO2). In order to investigate the synergy of metals iron and titanium in the SCR-NH3 reaction were prepared different materials ranging molar ratio Fe / Ti, synthesis method and titanium precursor. The chemical analysis of the samples showed small differences in the ratio Fe / Ti suggesting little loss of titanium and residual sulfur was observed for the sample that was prepared with TiOSO4. The X- ray diffraction indicated the formation of three phases (Fe2O3, TiO2 and Fe2TiO5) for all samples. The Rietveld refinement indicated the composition of each phase in each sample. The cell parameters suggested distortion suffered isomorphous substitution of both metals in the rutile structure (TiO2) and hematite (Fe2O3). The micrographs of the samples showed an agglomeration of distinct particles and forming pores in the samples prepared by combustion. The N2 adsorption isotherms showed materials with different textures and surface areas with 19 to 120 m² g-1. The temperature programmed desorption of ammonia shows that all the materials adsorb ammonia, a step of mechanism of the SCR-NH3 reaction. All prepared materials proved active in the SCR-NH3 reaction reaching 100% yield at 500 ° C. Stability tests were performed with two samples at temperatures of 350 to 450 ° C and both were stable material while maintaining or increasing the yield of N2. Study of reaction mechanism made by DRIFT showed that there is a greater formation of bands on the NH3 adsorption when compared to the adsorption of NO and thus the Eley-Rideal mechanism is more consistent for these materials. This study also assumed that the presence of O2 facilitates the adsorption of NH3. The catalyst prepared with TiOSO4 does not deactivate completely in the presence of SO2

This diploma work aims to evaluate the functional connection of the cogeneration unit with an internal combustion engine and an absorption heat pump to increase the heating effect of the cogeneration. The aim of this work is to design a functional system and evaluate it from the technical - economic terms. In the introduction of the theoretical work the applied cogeneration technologies used in combined heat and power production are presented. Then there is described the principle of heat pumps, their basic components and theoretical comparison of compression and absorption heat pumps. In the practical part of this work is for a specific application in the area Technická 2 proposed merger of the cogeneration unit with an internal combustion engine and an absorption heat pump, while detailed design parameters used in absorption heat circulation are set. At the end of this paper there are designed various heat exchangers of applied absorption heat pump. The final part of the work is devoted to technical - economic assessment of applied design. In this assestment three different types of heat pumps are compared: Absorption heat pump with working solution H2O-LiBR, absorption heat pump with working fluids NH3-H2O and compressor heat pump.

Deactivation of titania-supported vanadia commercial SCR catalysts exposed to flue gases from both coal and coal-biomass co-firing boilers were investigated. BET surface area and average pore diameter measurements on both fresh and exposed commercial catalyst samples indicated pore plugging occurred to exposed catalyst samples. ESEM analyses showed fouling on catalyst surface, and poison deposition on both catalyst surface and inner pores. Activity assessments of commercial monolith catalysts with various exposures (time and fuel type) indicated that catalyst deactivation involves fouling, pore plugging, and poisoning. Different mechanisms may dominate depending on exposure time, catalyst properties, and combustion environment. Better controlled lab-scale investigations involved poisoning and sulfation of SCR vanadia/titania catalysts synthesized with an incipient impregnation method. In situ FTIR spectroscopy indicate that K, Na, and Ca (among others materials) reduce, and sulfation and tungsten increase ammonia adsorption intensity on Brønsted acid sites. Activity measurements by MS showed K, Na, and Ca poison SCR catalysts, and sulfation and tungsten enhance SCR NOx reduction activity. Both the decrease and increase of catalyst activity arise from the decrease and increase of the pre-exponential factor (A) correspondingly. Moreover, the decrease of NO reduction activity from each poison are consistent with the IR peak area decrease of ammonia adsorbed on Brønsted acid site caused by the corresponding poison but not Lewis acid sites. Therefore, Brønsted acid sites participate more actively in SCR reaction than Lewis acid sites. However, Brønsted acid sites itself do not possess NOx reduction activity as indicated by zero NO conversion on 9% W/Ti which shows large amounts of Brønsted acid sites population. Therefore, dual acid (Brønsted) -redox (vanadia) sites are suggested to provide the active center during catalytic reduction cycle with weakly adsorbed or gas phase NOx reacts with surface adsorbed ammonia. In addition, in situ FTIR spectroscopy combined with XPS analyses indicate that sulfate does not form on vanadia sites but on titania sites.

A recent development for selective ammonia oxidation into nitrogen and water vapor (NH3-SCO) over noble metal-based catalysts is covered in the mini-review. As ammonia (NH3) can harm human health and the environment, it led to stringent regulations by environmental agencies around the world. With the enforcement of the Euro VI emission standards, in which a limitation for NH3 emissions is proposed, NH3 emissions are becoming more and more of a concern. Noble metal-based catalysts (i.e., in the metallic form, noble metals supported on metal oxides or ion-exchanged zeolites, etc.) were rapidly found to possess high catalytic activity for NH3 oxidation at low temperatures. Thus, a comprehensive discussion of property-activity correlations of the noble-based catalysts, including Pt-, Pd-, Ag- and Au-, Ru-based catalysts is given. Furthermore, due to the relatively narrow operating temperature window of full NH3 conversion, high selectivity to N2O and NOx as well as high costs of noble metal-based catalysts, recent developments are aimed at combining the advantages of noble metals and transition metals. Thus, also a brief overview is provided about the design of the bifunctional catalysts (i.e., as dual-layer catalysts, mixed form (mechanical mixture), hybrid catalysts having dual-layer and mixed catalysts, core-shell structure, etc.). Finally, the general conclusions together with a discussion of promising research directions are provided.

No description available.

Nanosized Cu-containing ZSM-5 catalysts with different n(Si)/ n(Al) ratio of 18.9–50.5 were prepared by ion-exchange. The physico-chemical characterization clearly shows that the molar ratio of framework T atoms influences the nature and distribution of copper species. According to DR UV-Vis, TPR-H2, EPR, or FT-IR spectroscopy analyses, the amount of aggregated copper species increases with increasing the framework n(Si)/n(Al) ratio. Thus, the activity of the Cu-containing ZSM-5 with n(Si)/n(Al) ratio of 47.0—50.5 in the selective catalytic NO reduction with NH3 (NH3-SCR-DeNOx) significantly decreases compared to the other materials (n(Si)/n(Al) ratio of 18.9—19.6). The reaction mechanism has been discussed in light of the results of 2D COS (two-dimensional correlation spectroscopy) analysis of IR spectra and catalytic properties of the zeolites. The results make evident that enhanced activity of Cu-containing ZSM-5 in NH3- SCR-DeNOx is correlated with the formation of different NOx under the experimental conditions.