A new concept of a "fiber sorbent" has been investigated. The fiber sorbent is produced as a pseudo-monolithic material comprising polymer (cellulose acetate, CA) and zeolite (NaY) by applying hollow fiber spinning technology. Phase separation of the polymer solution provides an appropriately porous structure throughout the fiber matrix. In addition, the zeolite crystals are homogeneously dispersed in the polymer matrix with high loading. The zeolite is the main contributor to sorption capacity of the fiber sorbent. Mass transfer processes in the fiber sorbent module are analyzed for hydrogen recovery and compared with results for an equivalent size packed bed with identical diameter and length. The model indicates advantageous cases for application of fiber sorbent module over packed bed technology that allows system downsizing and energy saving by changing the outer and bore diameters to maintain or even reduce the pressure drop. The CA-NaY fiber sorbent was spun successfully with highly porous structure and high CO2 sorption capacity. The fiber sorbent enables the shell-side void space for thermal moderation to heat of adsorption, while this cannot be applied to the packed bed. The poly(vinyl alcohol) coated CA-NaY demonstrated the thermal moderation with paraffin wax, which was carefully selected and melt at slightly above operating temperature, in the shell-side in a rapidly cycled pressure swing adsorption. So this new approach is attractive for some hydrogen recovery applications as an alternative to traditional zeolite pellets.

<p>Detta examensarbete är en förundersökning till Glafos undersökning angående rening av glasbrukens processvatten från antimon med zeolit.</p><p>Förundersökningen gick ut på att via experiment ta reda på hur mycket antimon som adsorberas av behandlad (för optimering: dels med NaNO3 och dels med NaCl) och obehandlad zeolit (porstorlek 0.4 nm). pH mättes och ställdes eftersom det har betydelse för adsorptionen, åtminstone vid väldigt lågt pH. När lösningarna hade filtrerats mättes den kvarvarande antimonhalten med atomabsorptionsspektrofotometri. Mätningarna visade att i genomsnitt 53 % av Sb-halten i lösningarna hade adsorberats av zeoliten. Förundersökningen visade att det inte blir någon adsorption då pH är väldigt lågt (under 1). Den visade också att när pH är över 4 verkar det inte ha någon betydelse om zeoliten är behandlad eller inte.</p><p>Zeoliten bör behandlas med NaCl först i en tank med omrörning, sedan blandas i processvattnet (vars pH justerats till pH 4) i en tank eller bassäng och därefter filtreras.</p><p>Tidsfaktorn för hur lång tid det tar för zeoliten att nå jämvikt och temperaturens inverkan bör även undersökas.</p> / <p>The aim of this diploma work is to study the removal of antimony from glassworks process water using zeolites.</p><p>The experimental part of the studies were carried out to find the quantity of antimony adsorbed by the zeolite. The studies included treated (for optimization: partly with NaNO3 and partly with NaCl) and untreated zeolite. The pore size is 0.4 nm. pH was measured and adjusted because it is important for the antimony adsorption. When the solutions were filtrated the content of antimony left was measured with atomic absorption spectrophotometry. The measurements showed an average uptake of antimony by the zeolite of 53 %.The preinvestigation indicates that with a very low pH (below 1) there is no antimony adsorption. It also indicates that with pH above 4 it does not matter if the zeolite are treated or not.</p><p>In further investigations the zeolite should be treated with NaCl in a stirred tank, then be mixed in the process water (pH is set to 4) in a tank or basin and then be filtrated.</p><p>The time to reach equilibrium and the influence of temperature should also be investigated.</p>

In this study, the feasibility of a NaA zeolite membrane for the gas phase separation of steam and hydrogen mixtures was determined. The Fischer-Tropsch (FT) process, which produces high value fuels and chemicals from coal and natural gas, can be greatly improved upon by the selective removal of water from the FT reactor product stream. According to the FT reaction kinetics, the rate of reaction increases with the partial pressure of hydrogen but is adversely affected the presence of water in the reactor product stream. Chemisorbed water on the surface of the metal catalysts also enhances deactivation due to sintering and fouling. The use of a zeolite membrane reactor is well equipped to serve the purpose of in-situ water removal as it can facilitate the separation of chemical components from one another in the presence of catalytic reactions. The LTA type zeolite membrane NaA or zeolite 4A, in particular, is well suited for the separation of polar (H2O) from non-polar (H2) molecules because of its high hydrophilicity. NaA has also been identified as an excellent candidate for selective water removal applications due its high adsorption affinity and capacity for water. The NaA membrane used in this study was manufactured by means of the in-situ crystallisation method where the growth of crystals on the inside surface of a centrifugally casted a-alumina support was favoured. Scanning electron microscopy (SEM) analyses performed on the membrane after a double hydrothermal synthesis indicated that the surface topology was rough and that the zeolite crystals formed were not uniform in size. Overall, the membrane thickness varied between 6.5 and 8.0 flm. An evaluation of the membrane quality was made possible through permeation experiments involving SF6 and Hz. The calculated Hz/SF6 permselectivity in this study was found to be 9.78, which despite being higher than the Knudsen diffusion selectivity of 8.54, confirmed the presence of intercrystalline defects or non-zeolitic pores in the membrane. Experiments concerning pure component and binary mixture permeation of steam and hydrogen through the supported NaA membrane were conducted over a temperature range of 115°C to 160 °c for binary hydrogen/steam mixtures, 25°C to 160°C for pure hydrogen and 130°C to 170°C for pure steam. For the permeation of pure component hydrogen, a local maximum in its permeance having a value of 224 x 10'°8 mol.m,z.s'!.Pa'! was reached at a system pressure and temperature of 6.875 bar and 75°C respectively. For the permeation of pure component steam through NaA, the effects of capillary condensation in the pores and defects of the zeolite membrane resulted in a decrease in steam permeance as a function of absolute pressure for temperatures lower than 160 °c. Once the effects of capillary condensation had receded, maxima in the steam permeances as a function of temperature corresponding to values of 70 x 10,08, 65 X 10,08 and 75 x 10,08 mol.m•2.s'I.Pa'l were found for the 182.5, 197.5 and 222.5 kPa isobars respectively. These observations collaborated well with the description of surface diffusion with permeation taking place in the Langmuir (strong adsorption) regime. Permeation experiments through NaA as function of temperature were conducted for a 90 mol% steam -10 mol% hydrogen (90-10) binary mixture as well as for a 60-40 mixture of these two. At low temperatures the permeation of hydrogen was completely suppressed by the condensed steam resulting in an almost perfect separation. The Kelvin equation was used to estimate the pore size of the defects which was found to range between 1.86 and 2.45 nm. The temperature range over which these defects in the membrane were assumed to become unblocked (i.e. assuming when the first breakthrough of hydrogen occurred), were determined to be between 140 to 148 °c and between 128 to 130 °c for the 90-10 and 60-40 mixtures respectively. The mixture selectivities (towards water) between 115 °c and 130 °c were found to be immensely high (much greater than 1000) for both the 90-10 and 60-40 mixtures, while the ideal selectivities were calculated to be less than lover the same temperature range. At 140 °c, the selectivity towards water for the 9010 mixture was still greater than 1000; however for the 60-40 mixture at this temperature, an inversion of selectivity towards H2 had already taken place. The breakthrough in H2 permeance occurs at a much lower temperature when the feed mixture contains a lower concentration of water. Since the partial pressure of steam will be reduced, larger pores will become unblocked at lower temperatures according to the Kelvin equation. / Thesis (M. Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2008.

This thesis examined the conversions of biomass and biomass components to petrochemicals and total aliphatic gasoline like products. There are three major projects of the thesis. Since biomass is very complicated, to understand the thermal decomposition pathways of biomass, the pyrolytic behaviors of various biomass components including lignin and cellulose under different reaction were investigated in the first phase. Due to complexity and limited volatility, the thermal decomposition products from biomass bring insurmountable obstacles to the traditional analysis methods such as GC-MS, UV and FT-IR. Therefore, precise characterization of the whole portion of thermal decomposition products has significant impacts on providing insight into the pyrolysis pathways and evaluating the upgrading processes. Various NMR methods to characterize different functional groups presented in liquid and solid pyrolysis products by 1H, 13C, 31P, 2D-HSQC and solid state 13C-NMR were introduced in the second phase. Nevertheless, the major drawback towards commercialization of pyrolysis oils are their challenging properties including poor volatility, high oxygen content, molecular weight, acidity and viscosity, corrosiveness and cold flow problems. In situ upgrading the properties of pyrolysis oils during thermal conversion process by employing zeolites has been discussed in the third phase. The further hydrogenation of pyrolysis oils to total aliphatic gasoline like products by heterogeneous catalysis in “green medium” – water has also been examined in the third project.

In this study, the feasibility of a NaA zeolite membrane for the gas phase separation of steam and hydrogen mixtures was determined. The Fischer-Tropsch (FT) process, which produces high value fuels and chemicals from coal and natural gas, can be greatly improved upon by the selective removal of water from the FT reactor product stream. According to the FT reaction kinetics, the rate of reaction increases with the partial pressure of hydrogen but is adversely affected the presence of water in the reactor product stream. Chemisorbed water on the surface of the metal catalysts also enhances deactivation due to sintering and fouling. The use of a zeolite membrane reactor is well equipped to serve the purpose of in-situ water removal as it can facilitate the separation of chemical components from one another in the presence of catalytic reactions. The LTA type zeolite membrane NaA or zeolite 4A, in particular, is well suited for the separation of polar (H2O) from non-polar (H2) molecules because of its high hydrophilicity. NaA has also been identified as an excellent candidate for selective water removal applications due its high adsorption affinity and capacity for water. The NaA membrane used in this study was manufactured by means of the in-situ crystallisation method where the growth of crystals on the inside surface of a centrifugally casted a-alumina support was favoured. Scanning electron microscopy (SEM) analyses performed on the membrane after a double hydrothermal synthesis indicated that the surface topology was rough and that the zeolite crystals formed were not uniform in size. Overall, the membrane thickness varied between 6.5 and 8.0 flm. An evaluation of the membrane quality was made possible through permeation experiments involving SF6 and Hz. The calculated Hz/SF6 permselectivity in this study was found to be 9.78, which despite being higher than the Knudsen diffusion selectivity of 8.54, confirmed the presence of intercrystalline defects or non-zeolitic pores in the membrane. Experiments concerning pure component and binary mixture permeation of steam and hydrogen through the supported NaA membrane were conducted over a temperature range of 115°C to 160 °c for binary hydrogen/steam mixtures, 25°C to 160°C for pure hydrogen and 130°C to 170°C for pure steam. For the permeation of pure component hydrogen, a local maximum in its permeance having a value of 224 x 10'°8 mol.m,z.s'!.Pa'! was reached at a system pressure and temperature of 6.875 bar and 75°C respectively. For the permeation of pure component steam through NaA, the effects of capillary condensation in the pores and defects of the zeolite membrane resulted in a decrease in steam permeance as a function of absolute pressure for temperatures lower than 160 °c. Once the effects of capillary condensation had receded, maxima in the steam permeances as a function of temperature corresponding to values of 70 x 10,08, 65 X 10,08 and 75 x 10,08 mol.m•2.s'I.Pa'l were found for the 182.5, 197.5 and 222.5 kPa isobars respectively. These observations collaborated well with the description of surface diffusion with permeation taking place in the Langmuir (strong adsorption) regime. Permeation experiments through NaA as function of temperature were conducted for a 90 mol% steam -10 mol% hydrogen (90-10) binary mixture as well as for a 60-40 mixture of these two. At low temperatures the permeation of hydrogen was completely suppressed by the condensed steam resulting in an almost perfect separation. The Kelvin equation was used to estimate the pore size of the defects which was found to range between 1.86 and 2.45 nm. The temperature range over which these defects in the membrane were assumed to become unblocked (i.e. assuming when the first breakthrough of hydrogen occurred), were determined to be between 140 to 148 °c and between 128 to 130 °c for the 90-10 and 60-40 mixtures respectively. The mixture selectivities (towards water) between 115 °c and 130 °c were found to be immensely high (much greater than 1000) for both the 90-10 and 60-40 mixtures, while the ideal selectivities were calculated to be less than lover the same temperature range. At 140 °c, the selectivity towards water for the 9010 mixture was still greater than 1000; however for the 60-40 mixture at this temperature, an inversion of selectivity towards H2 had already taken place. The breakthrough in H2 permeance occurs at a much lower temperature when the feed mixture contains a lower concentration of water. Since the partial pressure of steam will be reduced, larger pores will become unblocked at lower temperatures according to the Kelvin equation. / Thesis (M. Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2008.

Die hypocalcämische Gebärparese, insbesondere die subklinische Hypocalcämie, die oft nicht erkannt wird und Ursache vieler sekundär auftretender Folgeerkrankungen ist, stellt in der intensiven Milchviehhaltung ein bedeutendes Problem dar. Inzwischen gibt es eine Reihe verschiedener Vorbeugungsstrategien, wobei der Einsatz von Zeolith A als Ca-Binder in der Ration gegen Ende der Trächtigkeit eine relativ neue Präventionsmöglichkeit darstellt. Da zu diesem Futterzusatzstoff noch wenige Untersuchungen, insbesondere auf Nebeneffekte vorliegen, war das Ziel dieser Studien, den Einfluss von Zeolith A in verschiedenen Dosierungen auf die Futteraufnahme, den Energiestoffwechsel, die Futterverdaulichkeit und den Ca-, Mg- und P-Stoffwechsel sowie in hohen Dosierungen auch auf den Spurenelement-stoffwechsel zu untersuchen. Des Weiteren sollte untersucht werden, wie sich Zeolith A im Verdauungstrakt hinsichtlich der Freisetzung von Al verhält. In einer ersten Studie an 46 Kühen (≥ 3. Laktation), die in zwei Gruppen unterteilt wurden, wurde Zeolith A in einer Dosierung von 90 g/kg Trockensubstanz (T) in den letzten 2 Wochen der Trächtigkeit bis zum Kalbetag in eine totale Mischration (TMR), welche zur freien Aufnahme vorgelegt wurde, eingemischt. Die Zeolith A-Zulage ante partum zeigte peripartal eine stabilisierende Wirkung auf die Ca-Konzentration im Serum (> 2 mmol/l). Der Rückgang der Häufigkeit der Hypocalcämie (< 2 mmol/l) am Tag der Kalbung lag bei 76 %. Die mittlere Mg-Konzentration im Serum war bei den Kontrolltieren am Tag der Kalbung und 1 Tag post partum signifikant höher im Vergleich zu den Tieren der Versuchsgruppe, lag aber in beiden Gruppen im physiologischen Bereich (0,75-1,30 mmol/l). Auf die Spurenelement-konzentrationen (Cu, Zn, Mn und Fe) im Plasma wurde kein Zeolith A-Effekt festgestellt. Allerdings zeigten die Zeolith A-supplementierten Kühe ante partum einen signifikanten Rückgang in der Futteraufnahme, welche in einer negativen Energiebilanz mit einem signifi-kanten Anstieg der freien Fettsäuren und des Beta-Hydroxybutyrats im Serum resultierte. Dieser Effekt hatte allerdings keine Auswirkung auf die Futteraufnahme post partum und auf die Milchleistung in den ersten 105 Tagen der Folgelaktation. Des weiteren war die mittlere Konzentration des anorganischen Phosphats (Pi) bereits 7 Tage nach Beginn der Zeolith A-Zulage signifikant niedriger im Vergleich zu den Tieren der Kontrollgruppe und lag bis zum Tag der Kalbung deutlich unter der unteren physiologischen Grenze von 1,25 mmol/l. Die zweite Studie war ein Dosis-Wirkungsversuch an 80 Milchkühen (1.-7. Laktation) mit verschiedenen Zeolith A-Dosierungen (0, 12, 23 bzw. 43 g Zeolith A/kg T TMR). Dazu wurden die Tiere ca. 4 Wochen ante partum in 4 Gruppen und für die Untersuchung des Mineralstoffwechsel noch in zwei Untergruppen (1. + 2. Laktation bzw. ≥ 3. Laktation) unterteilt. Die Tiere erhielten eine TMR ad libitum vorgelegt. In den letzten zwei Wochen erhielten die Tiere Zeolith A in die Ration eingemischt. Eine Einmischung von 43 g Zeolith A/kg T TMR zeigte auf den Ca-, Mg- und Pi-Stoffwechsel sowie auf die Futteraufnahme und den Energiestoffwechsel vergleichbare Effekte wie in der ersten Studie bei einer Zulage von 90 g/kg T TMR. Eine Zeolith A-Zulage von 23 g/kg T TMR bei einem Zeolith A/Ca-Verhältnis von 5,6:1 hatte ebenfalls noch einen stabilisierenden Effekt auf den peripartalen Ca-Stoffwechsel (> 2 mmol/l) bei Kühen ≥ 3. Laktation, jedoch ohne markanten Rückgang in der Futteraufnahme. In dieser Tiergruppe war ein Rückgang der Häufigkeit der Hypocalcämie um 71 % zu verzeichnen. Diese Tiere zeigten auch nur eine moderate Hypophosphatämie. Eine Zeolith A-Zulage von 12 g/kg T TMR zeigte dagegen keine Effekte. In einem Stoffwechselversuch an 8 doppelt fistulierten Milchkühen (Pansen und proximales Duodenum) wurde schließlich der Einfluss von Zeolith A auf verdauungsphysiologische Para-meter und den Mineralstoffwechsel, insbesondere des Phosphors im Verdauungstrakt, sowie auf die Freisetzung von Al aus dem Zeolithverband untersucht. Die Tiere erhielten Mais- und Grassilage und Kraftfutter. Es wurde 0, 10 bzw. 20 g Zeolith A/kg T über einen Zeitraum von 3 Wochen mit dem Kraftfutter verabreicht. Eine Zeolith A-Zulage führte zu einer signifikant reduzierten scheinbaren ruminalen Verdaulichkeit der T sowie der ruminal fermentierten organischen Substanz. Allerdings waren in der fäkalen Ausscheidung der Nährstoffe keine signifikanten Unterschiede zwischen den Fütterungsgruppen festzustellen. Es zeigte sich kein Effekt auf die Ca- und Mg-Verdauung. Dagegen korrelierte die Konzentration des löslichen P im Pansen signifikant negativ mit der mittleren Zeolith A-Aufnahme. Des Weiteren hatten die Kühe mit einer Zeolith A-Zulage von 20 g/kg T eine signifikant höhere fäkale Ausscheidung des Gesamtphosphors im Vergleich zu den Tieren der Kontrollgruppe. Die herabgesetzte Bio-verfügbarkeit von P resultierte in einer signifikant erniedrigten Pi-Konzentration im Serum. Gleichzeitig war eine signifikant erhöhte Konzentration des gelösten Al im Pansen und ein signifikant höherer Fluss des gelösten Al im Duodenum festgestellt worden was auf eine Instabilität des Zeolithverbands beruht. Da eine Zeolith A-Dosierung von 12 g/kg T keinen Effekt auf den Ca-Stoffwechsel und eine Dosierung 43 g/kg T unerwünschte Effekte zeigte kann anhand dieser Untersuchungen geschlussfolgert werden, dass eine Einmischung in einem Bereich von 20 bis 30 g Zeolith A/kg T TMR, was bei einer mittleren täglichen T-Aufnahme von 10 kg ca. 200 bis 300 g Zeolith A/Tier/Tag entspricht, bei einem Zeolith A/Ca-Verhältnis von 6 bis 10:1 in der Ration in den letzten 2 Wochen der Trächtigkeit zur Vorbeugung der peripartalen Hypocalcämie zu empfehlen ist, ohne dass negative Effekte auf die Tiergesundheit zu erwarten sind. / Parturient paresis is known to be a frequent problem in high-yielding dairy cows. Subclinical hypocalcemia around calving is especially of particular importance, because it often remains undetected and may cause secondary diseases. In practice different preventive methods have been established, whereas feeding of zeolite A (synthetic sodium-aluminium-silikate) as a calcium binder in the last two weeks of pregnancy is a new strategy to prevent parturient hypocalcemia. However, there exists only little information about side effects of zeolite addition. The aim of this study was to investigate the influence of zeolite A, in several doses, on feed intake, energy metabolism, nutrient digestibility, as well as on calcium (Ca), magnesium (Mg) and phosphorus (P) metabolism, and in high doses on trace element metabolism. Further, it was to investigate the mechanism of zeolite A in the gastrointestinal tract, focused on releasing aluminium (Al). In a first study with 46 cows (≥ 3rd lactation) zeolite A was tested in a dose of 90 g/kg dry matter (DM) in the last two weeks of pregnancy. Therefore the cows were divided in two groups (control and zeolite supplemented group). All cows were fed a total mixed ration (TMR) ad libitum. The supplementation of zeolite A had a stabilising effect on Ca concentration in serum (> 2 mmol/l) around calving. The reduction of the hypocalcemia incidence (< 2 mmol/l) was 76 % on the day of calving. The Mg-concentration in serum was significantly higher for the cows without zeolite A supplementation compared to the cows of the experimental group on the day of calving and on the day after calving. However, the mean serum Mg concentration stayed in the physiological range (0.75-1.30 mmol/l) for both groups. No significant effect of the zeolite A supplementation was observed on the mean plasma concentration of trace elements (copper, zinc, manganese, iron). However, the zeolite A supplementation led to a significantly reduced feed intake ante partum, which resulted in a negative energy balance. Furthermore, non esterified fatty acid and beta-hydroxybutyrate in serum were increased significantly. However, no significant differences were observed in feed intake post partum as well as in milk yield in the first 105 days in the subsequent lactation between the two groups. Furthermore, zeolite A supplementation decreased significantly the concentration of inorganic phosphate (Pi) in serum. Seven days after beginning zeolite A supplementation, on the day of calving, the mean Pi-concentration was considerably below the physiological limit of 1.25 mmol/l. In the second study, zeolite A was tested in several lower doses. Therefore 80 dairy cows (1st – 7th lactation) were divided into four groups in the last 4 weeks of pregnancy. Additionally, the cows of each group were divided in two subgroups (1st + 2nd lactation and ≥ 3rd lactation) to determine the influence of zeolite A on mineral metabolism. All animals were fed a TMR ad libitum. In the last two weeks the cows received a daily dose of 0, 12, 23 and 43 g zeolite A/kg DM. Zeolite A supplementation of 43 g/kg DM showed comparable effects on Ca, Mg, and Pi metabolism, as well as on feed intake and energy metabolism as in the first study. For older cows (> 3rd lactation), supplementation of 23 g zeolite A/kg DM, and a zeolite A-Ca ratio of 5.6:1 resulted also in a stabilising effect on Ca metabolism (> 2 mmol/l) around calving without significant reduction of feed intake. The incidence of hypocalcemia was reduced by 71 %. The cows showed only a moderate hypophosphatemia. A zeolite A supplementation of 12 g did not have any preventive effects. In a metabolic-study with eight double fistulated dairy cows (rumen and proximal duodenum), the influence of zeolite A supplementation on several physiological parameters of digestion and on mineral metabolism, especially P in the rumino-intestinal-tract, was determined. Further releasing of Al from the zeolite structure was investigated. The cows were fed a maize/grass-silage (60:40 % based on DM) and concentrate. Several doses of zeolite A (0, 10 and 20 g/kg DM) were added to the concentrate over a period of three weeks. Zeolite A supplementation resulted in a significantly reduced ruminal digestibility of dry matter (DM) and fermentation of organic matter. No effect was observed on faecal digestion of DM and OM. Digestion of Ca and Mg in the rumino-intestinal tract was not influenced by zeolite A supplementation. However, the concentration of soluble P in rumen fluid correlated negatively with the mean zeolite A intake. The faecal excretion of total P increased significantly for cows with a zeolite A dose of 20 g/kg DM compared to the control group. The reduced bioavailability of P resulted in a significantly decreased concentration of Pi in serum. The zeolite A supplemented cows further showed a significantly higher concentration of soluble Al in rumen fluid as well as a significantly higher flow of soluble Al at the duodenum, which is a consequence of an instability of the zeolite structure. According to these results it can be concluded that a daily amount of 20 to 30 g zeolite A/kg DM, which complies a daily amount of 200 to 300 g zeolite A/cow at a daily DM intake of 10 kg, with a zeolite-Ca ratio of 6–10 to 1, for two weeks ante partum seems to be an adequate dose for reducing subclinical hypocalcemia in older cows without negative side effects on animal health. At an expected daily mean DM intake of 10 kg it is a daily amount of 200 to 300 g zeolite A/cow. A zeolite dose of 12 g/kg DM did not have any effect on Ca metabolism, and a dose of 43g/kg DM showed negative side effects.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-23T18:44:54Z No. of bitstreams: 1 JANAINA RAFAELLA SCHEIBLER - DISSERTAÇÃO PPGEQ 2015..pdf: 2465420 bytes, checksum: cbecc726b67d3d76a334570b655735eb (MD5) / Made available in DSpace on 2018-03-23T18:44:54Z (GMT). No. of bitstreams: 1 JANAINA RAFAELLA SCHEIBLER - DISSERTAÇÃO PPGEQ 2015..pdf: 2465420 bytes, checksum: cbecc726b67d3d76a334570b655735eb (MD5) Previous issue date: 2015 / Entre as membranas inorgânicas microporosas, as membranas zeolíticas constituem uma tecnologia promissora, devido às suas potenciais aplicações normalmente na desidratação do álcool, separação de moléculas de gás, separação de isômeros ou em processos químicos, incluindo reações de esterificação. Sob este aspecto, torna-se imprescindível o estudo das rotas de preparação desses materiais, visando desenvolver produtos com qualidade e a baixo custo. Portanto, a inovação deste estudo se dá na síntese de membranas zeolíticas via método de síntese poreplugging visando a utilização das membranas inorgânicas para permeação gasosa de N2. Neste trabalho foram desenvolvidos os seguintes materiais: zeólita ZSM-5, membranas cerâmicas (γ-alumina e α-alumina) e as membranas zeolíticas (ZSM5/γ-alumina e ZSM-5/α-alumina). A zeólita ZSM-5 foi sintetizada por meio do método hidrotérmico. As membranas cerâmicas (γ-alumina e α-alumina) foram preparadas a partir da técnica de conformação de pós cerâmicos e posteriormente submetidas à sinterização a uma temperatura de 1000 ºC/1h e 1200 ºC/1h respectivamente. A preparação das membranas zeolíticas (ZSM-5/γ-alumina e ZSM-5/α-alumina) foi realizada com base no método pore in plugging. As amostras foram caracterizadas a partir das técnicas de difração de raios X e Microscopia Eletrônica de Varredura. Os resultados experimentais permitem diversas conclusões acerca do desenvolvimento dos materiais: zeólita ZSM-5, membranas cerâmicas (γ-alumina e α-alumina) e membranas zeolíticas (ZSM-5/γ-alumina e ZSM-5/α-alumina). A partir da difração de raios X, foi possível verificar que o método de síntese empregado, foi efetivo na obtenção da zeólita ZSM-5. O difratograma apresentou picos característicos de uma zeólita ZSM-5 quando comparada ao padrão. Os resultados obtidos por DRX para as membranas cerâmicas (γ-alumina e α-alumina) demonstraram a formação de picos característicos do óxido de alumínio, os materiais são cristalinos e puros. Para o método pore-plugging pode se dizer que é um método promissor, pois mostrou uma formação satisfatória da camada zeolítica no resultado do DRX de ambas as membranas zeolíticas (ZSM-5/γ-alumina e ZSM-5/α-alumina). / Among the microporous inorganic membranes, zeolite membranes are a promising technology due to their potential applications normally in alcohol dehydration, separation of gas molecules, separation of isomers or chemical processes, including esterification reactions. In this regard, it is essential to study the preparation of these materials routes in order to develop products with quality and low cost. Therefore, innovation of this study gives the synthesis of zeolite membranes via pore-plugging synthesis method aimed at the use of inorganic membranes for gas permeation N2. In this work the following materials were developed: ZSM-5 zeolite, ceramic membranes (γ-alumina and α-alumina) and zeolitic membranes (ZSM-5/γ-alumina and ZSM-5/α-alumina). Zeolite ZSM-5 was synthesized by the hydrothermal method. Ceramic membranes (γ-alumina and α-alumina) were prepared from the ceramic powder forming technique, and subsequently subjected to a sintering temperature of 1000 °C/1h and 1200 °C/1h respectively. The preparation of zeolite membranes (ZSM-5/γ-alumina and ZSM-5/α-alumina) was carried out based on the method in pore plugging. The samples were characterized from the techniques of X diffraction and scanning electron microscopy rays. The experimental results allow several conclusions about the development of materials: zeolite ZSM-5, ceramic membranes (γ-alumina and α-alumina) and zeolite membranes (ZSM-5/γ-alumina and ZSM-5/αalumina). From the X-ray diffraction, it found that the method of synthesis used was effective in obtaining the zeolite ZSM-5. The XRD pattern showed peaks characteristic of ZSM-5 compared to the standard. The results obtained by XRD ceramic membranes (γ-alumina and α-alumina) showed the formation of peaks characteristic of aluminum oxide, the materials are crystalline and pure. For the poreplugging method can be said to be a promising method because it showed a satisfactory formation of the zeolite layer on the result of XRD both zeolite membranes (ZSM-5/γ-alumina and ZSM-5/α-alumina).

A presença de elevada carga nitrogenada em corpos hídricos pode causar sérios impactos ambientais como a eutrofização e a toxicidade do meio. Um dos processos que possibilitam a remoção de nitrogênio de efluentes é a adsorção, na qual o uso de adsorventes alternativos tem sido aplicado para o aproveitamento de resíduos e redução dos custos no processo. Dentro deste contexto, o processo de extração e beneficiamento do carvão fóssil na Região Sul do Brasil produz um rejeito (RB) com características que possibilitam sua aplicação na síntese de zeólitas, as quais podem ser utilizadas como adsorventes. Assim, o objetivo da presente tese foi avaliar a remoção do íon amônio de soluções aquosas por adsorção utilizando-se zeólitas naturais e sintetizadas a partir do rejeito RB. Em um primeiro momento, experimentos de adsorção foram conduzidos utilizando-se zeólita Na-clinoptilolita para conhecimento dos parâmetros termodinâmicos e da capacidade de regeneração do material. Posteriormente, a síntese de zeólitas utilizando rejeito RB foi realizada variando-se a fonte de alumínio, o emprego da agitação do meio durante a síntese e temperatura de calcinação do rejeito. A caracterização dos materiais foi feita através das técnicas de Difração de Raios X (DRX), Microscopia Eletrônica de Varredura acoplada a Espectroscopia por Dispersão em Energia (MEV-EDS), Potencial Zeta (PZ), Fluorescência de Raios X (FRX), Porosimetria de Nitrogênio (BET), Espectroscopia no Infravermelho por Transformada de Fourier (FTIR) e Capacidade de Troca Catiônica (CTC). Por fim, experimentos de adsorção de amônio foram feitos para o material que apresentou o maior conteúdo de íons sódio em sua composição. Quanto aos estudos com a Na-clinoptilolita, o estudo termodinâmico demostrou que a constante de equilíbrio (K0) da adsorção da zeólita estimada por diferentes métodos pode apresentar variação de até 105 de um método para outro. O estudo em questão também revelou que o método de Gaines e Thomas é o mais adequado para a estimativa dos parâmetros termodinâmicos. Nos testes de regeneração da zeólita utilizando-se solução NaCl de 0,5 a 3,0 M foram obtidos valores acima de 76% de regeneração para toda faixa de concentração avaliada, sem o reuso da solução de NaCl. Os testes feitos com o reuso da solução salina na etapa da dessorção permitiram concluir que é possível tratar até 160 mL de efluente utilizando-se somente 20 mL de solução NaCl 1,0 M, mantendo-se uma capacidade de adsorção equivalente a 80% da capacidade original da zeólita. Através da aplicação de diferentes condições de síntese utilizando o rejeito RB, foram obtidos sete diferentes materiais. O material que apresentou maior conteúdo de Na+ em sua composição foi obtido utilizando-se: pré-tratamento do rejeito com calcinação a 800 °C, síntese sem agitação do meio reacional e sem adição de fonte de alumínio. As análises do material indicaram formação de zeólitas dos tipos SOD e LTA. Quanto à adsorção de íons amônio, o mesmo apresentou capacidade de adsorção (qe) equivalente a 6,8 mg·g-1 (a 25ºC), que corresponde a 34 % do valor obtido para a Na-clinoptilolita, indicando que a síntese ainda necessita de melhoramentos para tornar o material mais competitivo frente à zeólita natural comercializada. / The presence of high nitrogen loading in water bodies can cause serious environmental impacts, such as eutrophication and toxicity of the medium. One of the process that enables nitrogen removal from effluents is adsorption, in which the use of alternative adsorbents have been applied in order to reuse wastes from other production processes and for lowering costs. Within this context, the coal mining and beneficiation in southern Brazil generates a waste with features that allow its application in zeolite synthesis. Thus, the objective of this thesis was to evaluate the removal of ammonium from aqueous solutions by adsorption using a natural zeolite and a zeolite synthesized from coal beneficiation tailings. Firstly, adsorption experiments were conducted using the natural zeolite Na-clinoptilolite in order to understand the thermodynamics and regeneration of process. Then, zeolite synthesis experiments using coal beneficiation tailings (RB) were conducted by varying the source of aluminum, stirring during crystallization step, and the calcination temperature applied to RB. The characterization of materials was made through the techniques of X-Ray Diffraction (XRD), Scanning Electron Microscopy coupled to Energy Dispersive Spectroscopy (SEM-EDS), Zeta Potential (ZP), X-rays Fluorescence (XRF), Porosimetry of Nitrogen (BET), Infrared Spectroscopy Fourier Transform (FTIR) and Cation Exchange Capacity (CEC). Finally, a test of ammonium adsorption was made with the material that had the highest content of Na+ in its composition. Regarding the studies with Na-clinoptilolite, the thermodynamic study showed that the equilibrium constant (K0) to adsorption process estimated through different approaches can present variation of up to 105 from one method to another. This study also revealed that the Gaines and Thomas method was the most adequate to the estimative of thermodynamic parameters. In the Na-clinoptilolite regeneration tests using NaCl solution from 0.5 to 3.0 M were obtained values above 76% regeneration to whole concentration range evaluated, without the reuse of NaCl solution. Tests made with the reuse of saline solution in the desorption step showed that it is possible to treat up to 160 mL of effluent using only 20 mL of NaCl solution, maintaining an adsorption capacity of 80 % of zeolite original capacity. By applying different synthesis conditions using the by-product of coal processing, seven different materials were obtained. The material with the highest content of Na+ was obtained using: calcination at 800°C as a thermal pretreatment applied to the waste, no stirring of the reaction during crystallization step and no additional aluminum source. The analysis of this material indicated formation of zeolites SOD and LTA. This same material was tested for the adsorption of ammonium, resulting in adsorption capacity (qe) of 6.8 m2·g-1, under the same conditions as the test with Na-clinoptilolite (at 25 ºC), which corresponds to 34 % of Na-clinoptilolite capacity, indicating that the synthesis still need some improvement in order to make the synthetic material competitive faced with the natural one.

Magister Scientiae (Medical Bioscience) - MSc(MBS) / The South African economy relies heavily on mining. The residues of these activities contain harmful metals that are discharged into the environment as industrial wastes, contaminating the air, soil, surface and ground water. A lot of people who live in remote areas in South Africa rely on ground water to drink and cook. They also cultivate their own vegetables increasing the risk of metal toxicity. Some of these metals are very toxic and can cause adverse effects upon being ingested. Toxic metals are well known to be harmful to humans. Some of these metals are carcinogenic or nephrotoxic when a large amount is accumulated in the human body causing cancer and destroying tissues such as the kidneys. The detrimental health effects of these metals may take months to years before manifestation causing people to sideline them as hazards. One of the major toxic elements that are discharged into the environment is lead. A natural zeolite called clinoptilolite has been widely used as an adsorbent for toxic metals from contaminated water and from the human body because of its properties such as ion-exchange capacity and pore size. However, this natural zeolite clinoptilolite is not pure and may contain traces of toxic elements of which the nature and concentration depend on the origin of clinoptilolite. The structural stability of clinoptilolite in acidic or alkaline media is not well documented. The lack of documented information about the leachates of clinoptilolite and their long term effects on the human body may cause harm to people who ingest this zeolite. This has led to investigation of synthetic zeolites such as faujasite which has already been used for decontamination of sludge, industrial effluents and other waste water by removing toxic metals such as Pb, Cd, Cu, Zn and As. This study focuses on comparing the toxic metal removal efficiency of natural zeolite clinoptilolite (C), clinoptilolite-based faujasite (FAU3) and clinoptilolite-based ultrastable Y zeolite (USY3), from contaminated water and simulated gastric juice containing lead and cadmium and to evaluate the extent of leaching of other elements from these zeolites. Clinoptilolite was used as a starting material for the synthesis of faujasite (FAU3) which was further treated with oxalic acid to get an ultrastable Y zeolite (USY3). Various techniques were used to characterise the as-received clinoptilolite, faujasite zeolite and USY, namely XRD, SEMEDS, FTIR, solid state NMR (27Al and 29Si) and BET-N2. These characterisation techniques confirmed that clinoptilolite was successfully transformed into faujasite and that the treatment of faujasite with oxalic acid yielded USY3. A comparative adsorption study was conducted using three zeolite samples: namely Clinoptilolite (C), clinoptilolite-based faujasite (FAU3) and ultrastable Y zeolite (USY3). ICP was used to characterise the liquid samples and it was concluded that zeolites were efficient in removing lead and cadmium from contaminated water samples as well as from simulated gastric juice. Some leachates from these zeolites were also observed. A contaminated water sample containing lead and cadmium was used as a medium where the removal capacity and percentage removal with C, FAU3 and USY3 was investigated. It was observed that the optimum dosage varied from one zeolite to the other and also from one metal to the other. The optimum dosage for C, FAU3 and USY3 for the uptake of lead was found to be 0.2 g, 0.2 g and 0.05 g respectively while for cadmium it was 0.4 g, 005 g and 0.1 g, respectively. It was also shown in this study that the removal capacity for lead and cadmium could be hindered by the Na content in FAU3 and USY3 due to the fact that these metals could be in an uptake competition with Na and other cations that leached out or exchanged from the zeolites. It was observed that the optimum metal concentration for lead uptake as well as for cadmium with few metals being released back into the solution was 0.1 mg/L. The optimum contact time for both lead and cadmium was 15 minutes. The factor that varied depending on the type of metal was pH, which was at its optimum at 3.5 for lead and at 5.5 for cadmium. A simulated gastric juice was contaminated with toxic metals (lead and cadmium) and the zeolites were used to treat the contaminated samples. It was shown that the removal capacity of these zeolites increased with the increase in initial concentration of the metal. Time proved to be one factor that affected the behaviour of zeolites. The modification of the synthesised faujasite into an ultrastable Y zeolite proved to have played a role in increasing the removal of toxic metals and in preventing the high leaching of some elements out of the zeolite. / 2018-12-14

Le travail de la thèse se focalise sur le traitement de l'air chargé en composés organiques volatils (COV) par un procédé d'ozonation avancée sur les zéolithes. Le procédé est basé sur la combinaison de deux techniques, utilisées de manière séquentielle : l'adsorption des COV sur un lit de zéolithes puis la régénération du lit saturé par ozonation. Avant d'étudier leur performance sur l'adsorption puis l'ozonation, les zéolithes ont été caractérisées par l'adsorption à l’azote, par spectroscopie Infra Rouge et par microscopie électronique. La concentration des sites acides de Lewis et de Brønsted ont également été quantifiées. Les interactions binaires entre le toluène et les zéolithes, puis entre l'ozone et les zéolithes sont étudiées. Les équilibres d'adsorption et les courbes de percées sur les différentes zéolithes sont déterminés expérimentalement, puis modélisés. La réactivité de l'ozone sur les zéolithes a été clarifiée, mettant en évidence la décomposition de l'ozone et la création d’espèces oxygénées oxydantes, adsorbées à la surface. L'influence de la concentration en sites acides de Lewis sur la décomposition de l’ozone a été discutée. Enfin, la régénération des adsorbants chargés en COV par l'ozone gazeux a été réalisée. L'influence des propriétés des zéolithes et des conditions opératoires ont été étudiées. / The PhD work focuses on the treatment of Organic Volatile Compound polluted air by an advanced ozonation process on hydrophobic zeolites. The process is based on two steps: gaseous pollutants are firstly adsorbed on zeolite bed; the second step is the regeneration of zeolites charged of COV by gaseous ozone. Firstly, zeolites are characterized by Nitrogen adsorption, analysis of Lewis and Brønsted acid sites, Infrared spectroscopy and Scanning Electron Microscopy. The adsorption equilibrium and breakthrough curve of toluene on different kind of zeolites are determined experimentally and modelled. The study of the reactivity of ozone on fresh zeolites shows that ozone is mainly decomposed on its surface and stable surface oxygenated species are produced. The latter can react with organic pollutant. The influence of Lewis acid site and operating conditions are discussed. Finally, the oxidation by ozone of toluene adsorbed on zeolites is realised. The comparison of zeolite structure and operating conditions (Air humidity, inlet ozone concentration) are carried out.