Seulonnan erotustehokkuuden määrittäminen - tarkastelussa Reichertin kartioseula

Seulonta on vanha ja teollisuudessa yleisesti käytetty erotusmenetelmä. Huolimat-ta yksinkertaisesta prosessista seulontaa ilmiönä on tutkittu vähän. Prosessin yk-sinkertaisuus on voinut osaltaan vaikuttaa tutkijoiden mielenkiintoon aihetta koh-taan. Tutkimuksen vähyys näkyy etenkin painovoimaiseen seulontaan liittyvän kirjallisuuden vähyytenä. Kirjallisuusosassa käsitellään seulonnan taustaa ja märkä- sekä kuivaseulontaa. Lisäksi määritetään seulontaan vaikuttavat tekijät ja kar-toitetaan seulontaan liittyvää matematiikkaa. Työn kokeellisessa osassa tutkitaan Reichertin kartioseulan erotustehokkuutta 10, 12,5 ja 15 asteen kallistuskulmissa. Tutkimukset tehdään ideaalisille pallomaisille lasihelmille. Mittaustulosten avulla tutkitaan myös partikkelien liikettä seulapin-nalla ja syötetyn massan vaikutusta erotustehokkuuteen. Kokeellisia mittaustulok-sia käytetään MATLAB-mallinnuksessa, jonka avulla optimoidaan kartioseulan kallistuskulmaa ja massapanosta suhteessa erotustehokkuuteen. Tutkimuksen kannalta olennaisia kysymyksiä ovat: ”Onko painovoimaan perustuva erottelu seuloilla riittävä takaamaan hyvän erotustehokkuuden?” ja ”Mikä on seulan ero-tustehokkuuden kannalta optimaalinen kallistuskulma ja syötettävä massa?” Reichertin kartioseulan etuja ovat sen energiatehokkuus ja yksinkertainen helposti säädettävä prosessi. Koemittauksista havaitaan, että erotustehokkuus vastaa opti-moinnin tuloksia. Seulan liian pieni kallistuskulma ja suuri massapanos pienentävät seulan erotustehokkuutta. Lisätutkimuksia tarvitaan eri kallistuskulmilla ja materiaaleilla, jotta tuloksia voidaan verrata todellisiin seulontaprosesseihin.

Sorção e dessorção do ametryn em Argissolo Vermelho-Amarelo e Latossolo Vermelho-Amarelo com diferentes valores de pH

Objetivou-se com este trabalho determinar os coeficientes de sorção e dessorção do ametryn num Argissolo Vermelho-Amarelo (PVA) e num Latossolo Vermelho-Amarelo (LVA) com diferentes valores de pH. Para isso, amostras desses solos foram coletadas na profundidade de 0 a 20 cm, em pastagens degradadas sem histórico da utilização de herbicidas da região de Viçosa, MG, e incubadas ou não com calcário por 90 dias. Neste estudo foi utilizado o método "Batch slurry", conduzido em condições controladas de laboratório. O método consistiu na utilização de 10,0 mL de solução com concentrações crescentes do padrão de ametryn, preparadas em solução de CaCl2 0,01 mol L-1, as quais foram adicionadas a 2,00 g de solo, permanecendo sob agitação rotatória por 12 h. Após centrifugação e filtração, a concentração do sobrenadante foi determinada pela técnica de cromatografia líquida de alta eficiência - CLAE, com detector UV de 245 nm. A dessorção foi avaliada utilizando as amostras contidas nos tubos, após os ensaios de sorção, que continham dose inicial de 25,0 mg L ¹ de herbicida. O PVA apresentou o maior coeficiente de adsorção (Kfa) quando comparado ao LVA, independentemente dos valores de pH das amostras. Isso foi atribuído ao maior teor de matéria orgânica do PVA em comparação ao LVA. Quando se compararam diferentes valores de pH utilizando apenas o LVA, observou-se que o aumento do pH ocasionou menor valor de Kfa. Baixos índices de histerese foram verificados no ametryn nos solos estudados, o que representa risco de lixiviação desse herbicida no perfil desses solos.

Sorption and desorption of picloram in soils under pastures in Brazil

The objective of this work was to determine the coefficients of sorption and desorption of picloram in Ultisol (PVA) and Oxisol (LVA), displaying different physical and chemical characteristics. Samples of soil were collected at the 0 20 cm depth in degraded pasture areas in Viçosa-MG. Firstly, the equilibrium time between the herbicide in solution and the herbicide which was sorbed in the soil was determined by the Batch Equilibrium method. The time required was 24 hours. Sorption and desorption studies were carried out under controlled laboratory conditions; the sorption evaluation consisted in adding 10.0 mL of herbicide solutions at different concentrations to tubes containing 2.00 g of soil, with vertical rotary agitation being maintained during the pre-determined equilibrium time. After centrifugation, supernatant extract cleaning and filtration, herbicide concentration was determined by high performance liquid chromatography (HPLC) with UV detection at 254 nm. Desorption was evaluated using the samples in the tubes after the sorption tests. The Freundlich model was used for interpretation of the sorption process. Ultisol showed higher adsorption coefficient (Kf a) compared with Oxisol, which may be attributed to the lower pH of the soil and its higher organic matter content. Desorption process occurred in both soils; the LVA allowed greater release of the previously sorbed molecules.

Sorção e dessorção do ametryn em Latossolos brasileiros

O conhecimento dos processos de retenção de herbicidas em solo é fundamental para se prever o potencial de lixiviação e degradação e a eficiência no controle das plantas daninhas. Objetivou-se com este trabalho avaliar os processos de sorção e dessorção do ametryn em quatro solos brasileiros: Latossolo Vermelho-Amarelo (LVA), Latossolo Vermelho-Amarelo húmico (LVAh), Latossolo Vermelho (LV) e Latossolo Amarelo (LA), com diferentes valores de pH. Para isso, utilizou-se o método Batch Equilibrium em condições controladas de laboratório e análise por cromatografia líquida de alta eficiência, com detector UV-Vis a 245 nm. Considerando os valores da constante de Freundlich modificada (K'f), verificou-se, entre os solos estudados, a ordem crescente de sorção do ametryn: LV pH 6,06 < LV pH 5,00 < LA pH 6,30 < LVA pH 6,11 < LVA pH 5,40 < LVAh pH 6,24 < LVAh pH 4,8. Conclui-se que as características teor de matéria orgânica e pH dos solos estudados afetaram a sorção e a dessorção do ametryn. Verificou-se também que solos com maiores teores de matéria orgânica foram os que apresentaram as maiores taxas de sorção, além das menores porcentagens de dessorção, indicando a ocorrência de histerese.

Sorção e dessorção do diuron em quatro latossolos brasileiros

O conhecimento do processo de sorção de herbicidas nos solos é uma das condições para fazer recomendações seguras do ponto de vista técnico e ambiental desses compostos. Neste trabalho, foram avaliadas a sorção e dessorção do diuron em Latossolo Vermelho-Amarelo (LVA), Latossolo Vermelho-Amarelo húmico (LVAh), Latossolo Vermelho (LV) e Latossolo Amarelo (LA), com diferentes valores de pH. Na avaliação da sorção e dessorção utilizou-se o método Batch Equilibrium, que consistiu na utilização de 10,0 mL de solução com concentrações de 0,5, 1, 2, 4, 8 e 15 mg L-1 do diuron, preparadas em CaCl2 0,01 mol L-1. Essas soluções foram adicionadas a amostras de 2,00 g de solo, permanecendo sob agitação por 12 horas. Após centrifugação e filtração, a concentração do diuron no sobrenadante foi determinada por cromatografia líquida de alta eficiência. A dessorção foi avaliada utilizando as amostras contidas nos tubos, após os ensaios de sorção, que continham dose inicial de 8 mg L-1 de herbicida. A isoterma de Freundlich ajustou-se adequadamente para descrever a sorção do diuron em todos os solos estudados. A sorção do diuron foi diretamente relacionada aos teores de matéria orgânica, visto que solos com maiores teores de matéria orgânica, LVA e LVAh, apresentaram maiores coeficientes de sorção. O aumento do pH dos solos elevou a sorção do diuron, de forma mais evidente no LV, sendo este o solo que apresentou o menor teor de matéria orgânica. O processo de dessorção do diuron foi inverso ao da sorção, pois solos com menor sorção apresentaram as maiores porcentagens de dessorção.

Novel technology for preparation of optically active chemicals

Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.

Sorption and desorption of Suflafenacil in two soils in the state of São Paulo with different physical and chemical attributes

A study was conducted to evaluate the sorption and desorption of 14C herbicide saflufenacil (pyrimidinedione) in two soils in the State of São Paulo, classified as Red Yellow Latosol with clayey texture (LVA-1) and medium texture (LVA-2), using the batch method through isotherms. The soils were air dried and sieved a 2 mm mesh. The radioactivity was determined by liquid scintillation spectrometry in acclimatized room (25 ± 2 °C). Sorption isotherms were conducted for 5 concentrations of saflufenacil (5.0; 2.5; 1.0; 0.5 and 0.05 μg mL-1) and the results were adjusted to the Freundlich equation, thus obtaining the parameters of sorption followed by two extractions with 0.01 M CaCl2 to determine desorption parameters similarly to sorption. The results showed that saflufenacil sorption was low for both soils studied, being greater for the LVA with higher organic matter content. The desorption coefficients were greater than their sorption coefficients, suggesting the occurrence of hysteresis. The sorption and desorption isotherms (classified as type C isotherms), hysteresis and the t-test between the angular coefficient of the respective isotherms showed that both the sorption and desorption occur with equal intensity.

Issues with Fedora & Hydra, experiences from a research-data-driven implementation

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

DSpace for Data Revisited

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

A Distributed Microservices Framework Integrating Taverna

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

AOD 2.0: A category based submission add-on for DSpace 4.0

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Effect of nitrate and ammonium on the growth and protein concentration of Microcystis viridis Lemmermann (Cyanobacteria)

Cyanobacteria are a very important group in aquatic systems, particularly in eutrophic waters. Therefore studies about their success in the environment are essential. Many hypotheses have tried to explain the dominance of Cyanobacteria, and several emphasized the importance of various nitrogen sources for the success of the group. In this study, we measured the effect of ammonium and nitrate on the growth and protein concentration of Microcystis viridis (Cyanobacteria). This species is well-known because bloom formation in eutrophic waters. The study was carried out, in experimental batch cultures, using the WC medium with different nitrogen sources: ammonium, nitrate, ammonium + nitrate (50% ammonium + 50% nitrate) and ammonium at different concentrations (to test for possible NH4+ toxicity). Protein, ammonium and nitrate concentrations were measured at end of each experiment, whereas samples for cell counts were taken daily. Results showed that Microcystis viridis grew faster with ammonium (µ = 0.393 day-1) than with nitrate (µ = 0.263 day-1) and ammonium + nitrate (µ = 0.325 day-1). This pattern is explained by the metabolism of ammonium that presents higher uptake and assimilation rates than nitrate. Maximum cell concentration, however, was higher in the ammonium + nitrate treatment, followed by nitrate treatment. Higher protein concentration were observed in the treatment with nitrate. In the ammonium toxicity test, no difference between the control and NH4+ at 50% was found. Thus, the ammonium concentrations used in these experiments were not toxic. Our results suggest that Cyanobacteria is able to grow on both nitrogen sources even if ammonium may allow faster growth and bloom development.

Purification of Hydrocarbon Waste Streams

Purification of hydrocarbon waste streams is needed to recycle valuable hydrocarbon products, reduce hazardous impacts on environment, and save energy. To obtain these goals, research must be focused on the search of effective and feasible purification and re-refining technologies. Hydrocarbon waste streams can contain both deliberately added additives to original product and during operation cycle accumulated undesired contaminants. Compounds may have degenerated or cross-reacted. Thus, the presence of unknown species cause additional challenges for the purification process. Adsorption process is most suitable to reduce impurities to very low concentrations. Main advantages are availability of selective commercial adsorbents and the regeneration option to recycle used separation material. Used hydrocarbon fraction was purified with various separation materials in the experimental part. First screening of suitable materials was done. In the second stage, temperature dependence and adsorption kinetics were studied. Finally, one fixed bed experiment was done with the most suitable material. Additionally, FTIR-measurements of hydrocarbon samples were carried out to develop a model to monitor the concentrations of three target impurities based on spectral data. Adsorption capacities of the tested separation materials were observed to be low to achieve high enough removal efficiencies for target impurities. Based on the obtained data, batch process would be more suitable than a fixed bed process and operation at high temperatures is favorable. Additional pretreatment step is recommended to improve removal efficiency. The FTIR-measurement was proven to be a reliable and fast analysis method for challenging hydrocarbon samples.

Modified nano- and microcellulose based adsorption materials in water treatment

In recent decades, industrial activity growth and increasing water usage worldwide have led to the release of various pollutants, such as toxic heavy metals and nutrients, into the aquatic environment. Modified nanocellulose and microcellulose-based adsorption materials have the potential to remove these contaminants from aqueous solutions. The present research consisted of the preparation of five different nano/microcellulose-based adsorbents, their characterization, the study of adsorption kinetics and isotherms, the determination of adsorption mechanisms, and an evaluation of adsorbents’ regeneration properties. The same well known reactions and modification methods that were used for modifying conventional cellulose also worked for microfibrillated cellulose (MFC). The use of succinic anhydride modified mercerized nanocellulose, and aminosilane and hydroxyapatite modified nanostructured MFC for the removal of heavy metals from aqueous solutions exhibited promising results. Aminosilane, epoxy and hydroxyapatite modified MFC could be used as a promising alternative for H2S removal from aqueous solutions. In addition, new knowledge about the adsorption properties of carbonated hydroxyapatite modified MFC as multifunctional adsorbent for the removal of both cations and anions ions from water was obtained. The maghemite nanoparticles (Fe3O4) modified MFC was found to be a highly promising adsorbent for the removal of As(V) from aqueous solutions due to its magnetic properties, high surface area, and high adsorption capacity . The maximum removal efficiencies of each adsorbent were studied in batch mode. The results of adsorption kinetics indicated very fast removal rates for all the studied pollutants. Modeling of adsorption isotherms and adsorption kinetics using various theoretical models provided information about the adsorbent’s surface properties and the adsorption mechanisms. This knowledge is important for instance, in designing water treatment units/plants. Furthermore, the correspondence between the theory behind the model and properties of the adsorbent as well as adsorption mechanisms were also discussed. On the whole, both the experimental results and theoretical considerations supported the potential applicability of the studied nano/microcellulose-based adsorbents in water treatment applications.

Catalytic direct synthesis of hydrogen peroxide in a novel microstructured reactor

The direct synthesis from hydrogen and oxygen is a green alternative for production of hydrogen peroxide. However, this process suffers from two challenges. Firstly, mixtures of hydrogen and oxygen are explosive over a wide range of concentrations (4-94% H2 in O2). Secondly, the catalytic reaction of hydrogen and oxygen involves several reaction pathways, many of them resulting in water production and therfore decreasing selectivity. The present work deals with these two challenges. The safety problem was dealed by employing a novel microstructured reactor. Selectivity of the reaction was highly improved by development a set of new catalysts. The final goal was to develop an effective and safe continuous process for direct synthesis of hydrogen peroxide from H2 and O2. Activated carbon cloth and Sibunit were examined as the catalysts’ supports. Palladium and gold monometallic and palladium-gold bimetallic catalysts were thoroughly investigated by numerous kinetic experiments performed in a tailored batch reactor and several catalyst charachterization methods. A complete set of data for direct synthesis of H2O2 and its catalytic decomposition and hydrogenation was obtained. These data were used to assess factors influencing selectivity and activity of the catalysts in direct synthesis of H2O2 as well as its decomposition and hydrogenation. A novel microstructured reactor was developed based on hydrodynamics and mass transfer studies in prototype microstractural plates. The shape and the size of the structural elements in the microreactor plate were optimized in a way to get high gas-liquid interfacial area and gas-liquid mass transfer. Finally, empirical correlations for the volumetric mass transfer coefficient were derived. A bench-scale continuous process was developed by using the novel microstructral plate reactor. A series of kinetic experiments were performed to investigate the effects of the gas and the liquid feed rates and their ratio, the amount of the catalyst, the gas feed composition and pressure on the final rate of H2O2 production and selectivity.