882 resultados para trihydrogen cation (H3 )
Resumo:
Denna vrdvetenskapliga avhandling syftar till att avtcka och belysa en vrdande och helande dimension vid existentiellt lidande patienters mten med bildkonst inom vrdkontext. Kunskapsskandet sker i tv studier. Den frsta (studie I) r en ikonografi sk tolkning av konstnren Matthias Grnewalds (ca 14601528) senmedeltida altarskpsmlningar. I studien uttolkas lidandets uttryck och narrativa budskap samt symboliska gestaltningar av vrdande och helande i valda delar av detta s.k. Isenheimaltares bildprogram. Tolkningen utgr frn rekonstruktionen av altarskpets ursprungskontext, det medeltida Isenheimklostret, dr svrt sjuka och dende patienter vrdades. I studie tv (II) fortstter skandet i den moderna hospicevrdens kontext med hjlp av en kvalitativ intervjustudie som utforskar patienters meningsskapande vid mten med sjlvvald bildkonst (oljemlningar och akvareller av fi nlndska konstnrer som donerats till det sjukhus dr intervjustudien gjordes). Forskningsansatsen r inspirerad av Hans-Georg Gadamers (19012002) hermeneutik. Vidare anvnds ngra nyare tolkningsteoretiska ansatser inom bildkonstens omrde. Forskningens tolkningsresultat visar att bildkonsten har potentialer svl p ett miljestetiskt plan som p en djupare individuell symbolniv. Som designkomponent i vrdmiljns rumsliga gestaltning bygger bildkonsten in estetiska, etiska och andliga kvaliteter utifrn tidsmssiga och kulturella koder. I den medeltida klostervrdens kontext sammanfll bildkonstens dekorativa betydelse med andliga och helande syften. Nr det gller sjlvvalda konstverk i den moderna vrdkontexten bidrar de till det enskilda patientrummets atmosfr p ett unikt stt utifrn patientens personlighet och behov. P en frdjupad mtesniv, i samspel med bildens symboliska funktion, sker en inlevelsemssig frfl yttning in i bildens vrld. Betraktarens inlevelse aktiveras till en transcenderande rrelse som gr bortom det faktiska rummets och den reella tidens grnser. Vid resor i konstens bildvrld spelas minnesvrda hndelser upp frn det frgngna, men ven framtiden kommer betraktaren till mtes. I en existentiell livssituation sker mnniskan i konstverkets bildinnehll efter symbolisk mening som kan ge svar p lidandets frgor. Bilderna iscenstter d helande motbilder som utgr korrektiv i symboliska former nr olika existentiella frluster hotar. Nr livet frbleknats av sjukdom besvarar bildvrlden den lidandes blick med lysande violer som blommar upp, ger livskraft och bekrftar personens vrdighet mitt i det frvissnande mnniskolivet. Nr ngest och otrygghet nalkas inbjuds betraktaren till besk i landskap som utvidgar sjukhusrummets vggar mot hemgrdens trygghet. Dr livet hotas av frgnglighet tar bildvrlden mnniskan med sig till naturens eviga terfdelse. Upplevelsen av att vara delaktig i ett strre och heligt sammanhang ppnar vgen ut ur lidandets avskurenhet. I medeltidens vrdkontext erbjd den sakrala bilden en kollektiv och helande Symbolon som genom sin representationskraft synliggjorde det osynliga. Vid bildmten i den moderna hospicevrdens kontext var det naturteman som glntade p drren till det hemliga rummet i djupet av hjrtat. Forskningen antyder att ven om meningsskapandet i ett bildmte r avhngigt tidsepok, betraktarens frfrstelse och kulturella kontext samt typen av bilder kan bildsymboliken, generellt frstdd som den saknade formen eller det saknade livssammanhanget, framvisa en helande och hoppingivande ordning i lidandets kaos.
Resumo:
This thesis is devoted to growth and investigations of Mn-doped InSb and II-IV-As2 semiconductors, including Cd1-xZnxGeAs2:Mn, ZnSiAs2:Mn bulk crystals, ZnSiAs2:Mn/Si heterostructures. Bulk crystals were grown by direct melting of starting components followed by fast cooling. Mn-doped ZnSiAs2/Si heterostructures were grown by vacuum-thermal deposition of ZnAs2 and Mn layers on Si substrates followed by annealing. The compositional and structural properties of samples were investigated by different methods. The samples consist of micro- and nano- sizes clusters of an additional ferromagnetic Mn-X phases (X = Sb or As). Influence of magnetic precipitations on magnetic and electrical properties of the investigated materials was examined. With relatively high Mn concentration the main contribution to magnetization of samples is by MnSb or MnAs clusters. These clusters are responsible for high temperature behavior of magnetization and relatively high Curie temperature: up to 350 K for Mn-doped II-IV-As2 and about 600 K for InMnSb. The low-field magnetic properties of Mn-doped II-IV-As2 semiconductors and ZnSiAs2:Mn/Si heterostructures are connected to the nanosize MnAs particles. Also influence of nanosized MnSb clusters on low-field magnetic properties of InMnSb have been observed. The contribution of paramagnetic phase to magnetization rises at low temperatures or in samples with low Mn concentration. Source of this contribution is not only isolated Mn ions, but also small complexes, mainly dimmers and trimmers formed by Mn ions, substituting cation positions in crystal lattice. Resistivity, magnetoresistance and Hall resistivity properties in bulk Mn-doped II-IV-As2 and InSb crystals was analyzed. The interaction between delocalized holes and 3d shells of the Mn ions together with giant Zeeman splitting near the cluster interface are respond for negative magnetoresistance. Additionally to high temperature critical pointthe low-temperature ferromagnetic transition was observed Anomalous Hall effect was observed in Mn doped samples and analyzed for InMnSb. It was found that MnX clusters influence significantly on magnetic scattering of carriers.
Resumo:
Percarboxylic acids are commonly used as disinfection and bleaching agents in textile, paper, and fine chemical industries. All of these applications are based on the oxidative potential of these compounds. In spite of high interest in these chemicals, they are unstable and explosive chemicals, which increase the risk of synthesis processes and transportation. Therefore, the safety criteria in the production process should be considered. Microreactors represent a technology that efficiently utilizes safety advantages resulting from small scale. Therefore, microreactor technology was used in the synthesis of peracetic acid and performic acid. These percarboxylic acids were produced at different temperatures, residence times and catalyst i.e. sulfuric acid concentrations. Both synthesis reactions seemed to be rather fast because with performic acid equilibrium was reached in 4 min at 313 K and with peracetic acid in 10 min at 343 K. In addition, the experimental results were used to study the kinetics of the formation of performic acid and peracetic acid. The advantages of the microreactors in this study were the efficient temperature control even in very exothermic reaction and good mixing due to the short diffusion distances. Therefore, reaction rates were determined with high accuracy. Three different models were considered in order to estimate the kinetic parameters such as reaction rate constants and activation energies. From these three models, the laminar flow model with radial velocity distribution gave most precise parameters. However, sulfuric acid creates many drawbacks in this synthesis process. Therefore, a greener way to use heterogeneous catalyst in the synthesis of performic acid in microreactor was studied. The cation exchange resin, Dowex 50 Wx8, presented very high activity and a long life time in this reaction. In the presence of this catalyst, the equilibrium was reached in 120 second at 313 K which indicates a rather fast reaction. In addition, the safety advantages of microreactors were investigated in this study. Four different conventional methods were used. Production of peracetic acid was used as a test case, and the safety of one conventional batch process was compared with an on-site continuous microprocess. It was found that the conventional methods for the analysis of process safety might not be reliable and adequate for radically novel technology, such as microreactors. This is understandable because the conventional methods are partly based on experience, which is very limited in connection with totally novel technology. Therefore, one checklist-based method was developed to study the safety of intensified and novel processes at the early stage of process development. The checklist was formulated using the concept of layers of protection for a chemical process. The traditional and three intensified processes of hydrogen peroxide synthesis were selected as test cases. With these real cases, it was shown that several positive and negative effects on safety can be detected in process intensification. The general claim that safety is always improved by process intensification was questioned.
Resumo:
Banana is the most consumed fruit in the world and Brazil is the second largest producer. Despite its global position, Brazil has an average of 40% losses during the post-harvest period. So, this experiment aimed at evaluating the efficiency of post-harvest treatments to improve the storage of banana cultivars cv. 'Prata', 'Ma' and 'Nanica'. The fruits were acquired at CEASA with green peel, and were submitted to six different treatments: T- immersion in drinking water for 3 minutes (control), H3 - hot water (50 C for 3 minutes), H8 - hot water (50 C for 8 minutes), HP - immersion in hypochlorite 0.2% for 3 minutes, OS - immersion in soybean oil 10% for 3 minutes, and OM - immersion in mineral oil 10% for 3 minutes. The fruits were stored at room temperature at about 21 C for 14 days and evaluated in three periods (1, 7 and 14 days) comparing peel color, flesh/peel ratio, titratable acidity (TA), soluble solids (SS), SS/TA ratio, and pH. The fruits of cv. 'Prata' and 'Ma' submitted to the treatments H3, H8 and HP ripened at the same time as the control for peel color, which showed increased soluble solids, flesh/peel ratio, acidity and a decrease in pH. On the other hand, the cv. 'Nanica' did not respond significantly different when compared to the applied treatments and the control. The fruits treated with OM and OS were kept green for a longer time for the cultivars 'Prata' and 'Nanica', but there were some changes on peel color due dark spots in 'Prata' banana and a softening aspect in 'Nanica', indicating some level of toxicity of these treatments. Fruits of the 'Ma' cultivar continued green with the application of mineral oil, without toxicity symptoms. In conclusion, the treatments applied did not show any advantage for storage of these fruits.
Resumo:
The potassium ion, present in great amount in the vinasse because it is a monovalent cation, has the characteristic of promoting the dispersion of clay particles, in the same way as the sodium, causing a reduction in the pore space of the soil and, in its turn, reducing its permeability. To evaluate this effect of reduction by application of vinasse to the soil, an experiment was conducted for three different soils, with the objective of evaluating the effect of the application of different doses of vinasse on hydraulic conductivity of saturated soil and verifying its possible chemical changes of these soils. For that, it was used PVC columns (in a scheme of constant head permeameter to obtain the values of hydraulic conductivity of saturated soil), filled with three soils - Dark Red Latosol (DRL), Purple Latosol (PL) and Eutrophic Red Nitossol (ERN) - , in which were applied four doses of vinasse (0, 150, 300 and 450m ha-1), distributed in a completely randomized design with a 3x4 factorial scheme with three replications. The results evidenced that only the Dark Red Latosol (DRL) showed a reduction in the values of hydraulic conductivity of saturated soil, and in front of the application of vinasse, up to 300m ha-1, it was observed an increase in the concentrations of potassium, calcium and cation exchange capacity (CEC) ions.
Resumo:
Nitrate is the main form of nitrogen associated with water contamination; the high mobility of this species in soil justifies the concern regarding nitrogen management in agricultural soils. Therefore, the objective of this research was to assess the effect of companion cation on nitrate displacement, by analyzing nitrate transport parameters through Breakthrough Curves (BTCs) and their settings made by numerical model (STANMOD). The experiment was carried out in the Soil and Water Quality Laboratory of the Department of Biosystems Engineering, "Luiz de Queiroz" College of Agriculture in Piracicaba (SP), Brazil. It was performed using saturated soil columns in steady-state flow condition, in which two different sources of inorganic nitrate Ca(NO3)2 and NH4NO3 were applied at a concentration of 50 mg L-1 NO3-. Each column was filled with either a Red-Yellow Oxisol (S1) or an Alfisol (S2). Results are indicative that the companion ion had no effect on nitrate displacement. However, nitrate transport was influenced by soil texture, particle aggregation, solution speed in soil and organic matter presence. Nitrate mobility was higher in the Alfisol (S2).
Resumo:
In this thesis, a classi cation problem in predicting credit worthiness of a customer is tackled. This is done by proposing a reliable classi cation procedure on a given data set. The aim of this thesis is to design a model that gives the best classi cation accuracy to e ectively predict bankruptcy. FRPCA techniques proposed by Yang and Wang have been preferred since they are tolerant to certain type of noise in the data. These include FRPCA1, FRPCA2 and FRPCA3 from which the best method is chosen. Two di erent approaches are used at the classi cation stage: Similarity classi er and FKNN classi er. Algorithms are tested with Australian credit card screening data set. Results obtained indicate a mean classi cation accuracy of 83.22% using FRPCA1 with similarity classi- er. The FKNN approach yields a mean classi cation accuracy of 85.93% when used with FRPCA2, making it a better method for the suitable choices of the number of nearest neighbors and fuzziness parameters. Details on the calibration of the fuzziness parameter and other parameters associated with the similarity classi er are discussed.
Resumo:
Ion exchange membranes are indispensable for the separation of ionic species. They can discriminate between anions and cations depending on the type of fixed ionic group present in the membrane. These conventional ion exchange membranes (CIX) have exceptional ionic conductivity, which is advantageous in various electromembrane separation processes such as electrodialysis, electrodeionisation and electrochemical ion exchange. The main disadvantage of CIX membranes is their high electrical resistance owing to the fact that the membranes are electronically non conductive. An alternative can be electroactive ion exchange membranes, which are ionically and electronically conducting. Polypyrrole (PPy) is a type of electroactive ion exchange material as well as a commonly known conducting polymer. When PPy membranes are repeatedly reduced and oxidised, ions are pumped through the membrane. The main aim of this thesis was to develop electroactive cation transport membranes based on PPy for the selective transport of divalent cations. Membranes developed composed of PPy films deposited on commercially available support materials. To carry out this study, cation exchange membranes based on PPy doped with immobile anions were prepared. Two types of dopant anions known to interact with divalent metal ions were considered, namely 4-sulphonic calix[6]arene (C6S) and carboxylated multiwalled carbon nanotubes (CNT). The transport of ions across membranes containing PPy doped with polystyrene sulphonate (PSS) and PPy doped with para-toluene sulphonate (pTS) was also studied in order to understand the nature of ion transport and permeability across PPy(CNT) and PPy(C6S) membranes. In the course of these studies, membrane characterisation was performed using electrochemical quartz crystal microbalance (EQCM) and scanning electron microscopy (SEM). Permeability of the membranes towards divalent cations was explored using a two compartment transport cell. EQCM results demonstrated that the ion exchange behaviour of polypyrrole is dependent on a number of factors including the type of dopant anion present, the type of ions present in the surrounding medium, the scan rate used during the experiment and the previous history of the polymer film. The morphology of PPy films was found to change when the dopant anion was varied and even when the thickness of the film was altered in some cases. In nearly all cases the permeability of the membranes towards metal ions followed the order K+ > Ca2+ > Mn2+. The one exception was PPy(C6S), for which the permeability followed the order Ca2+ K+ > Mn2+ > Co2+ > Cr3+. The above permeability sequences show a strong dependence on the size of the metal ions with metal ions having the smallest hydrated radii exhibiting the highest flux. Another factor that affected the permeability towards metal ions was the thickness of the PPy films. Films with the least thickness showed higher metal ion fluxes. Electrochemical control over ion transport across PPy(CNT) membrane was obtained when films composed of the latter were deposited on track-etched Nucleopore membranes as support material. In contrast, the flux of ions across the same film was concentration gradient dependent when the polymer was deposited on polyvinylidene difluoride membranes as support material. However, electrochemical control over metal ion transport was achieved with a bilayer type of PPy film consisting of PPy(pTS)/PPy(CNT), irrespective of the type of support material. In the course of studying macroscopic charge balance during transport experiments performed using a two compartment transport cell, it was observed that PPy films were non-permselective. A clear correlation between the change in pH in the receiving solution and the ions transported across the membrane was observed. A decrease in solution pH was detected when the polymer membrane acted primarily as an anion exchanger, while an increase in pH occurred when it functioned as a cation exchanger. When there was an approximately equal flux of anions and cations across the polymer membrane, the pH in the receiving solution was in the range 6 - 8. These observations suggest that macroscopic charge balance during the transport of cations and anions across polypyrrole membranes was maintained by introduction of anions (OH-) and cations (H+) produced via electrolysis of water.
Resumo:
The general trend towards increasing e ciency and energy density drives the industry to high-speed technologies. Active Magnetic Bearings (AMBs) are one of the technologies that allow contactless support of a rotating body. Theoretically, there are no limitations on the rotational speed. The absence of friction, low maintenance cost, micrometer precision, and programmable sti ness have made AMBs a viable choice for highdemanding applications. Along with the advances in power electronics, such as signi cantly improved reliability and cost, AMB systems have gained a wide adoption in the industry. The AMB system is a complex, open-loop unstable system with multiple inputs and outputs. For normal operation, such a system requires a feedback control. To meet the high demands for performance and robustness, model-based control techniques should be applied. These techniques require an accurate plant model description and uncertainty estimations. The advanced control methods require more e ort at the commissioning stage. In this work, a methodology is developed for an automatic commissioning of a subcritical, rigid gas blower machine. The commissioning process includes open-loop tuning of separate parts such as sensors and actuators. The next step is to apply a system identi cation procedure to obtain a model for the controller synthesis. Finally, a robust model-based controller is synthesized and experimentally evaluated in the full operating range of the system. The commissioning procedure is developed by applying only the system components available and a priori knowledge without any additional hardware. Thus, the work provides an intelligent system with a self-diagnostics feature and an automatic commissioning.
Resumo:
Tyss tutkittiin lignoselluloosapohjaisten vkevhappohydrolysaattien (monosakkaridit, rikki- ja etikkahppo) jatkuvatoimista kromatografista fraktiointia kytten Japan Organo SMB -prosessia. Adsorbenttin toimi happomuotoinen (H+) vahva kationinvaihtohartsi. Panostoimista fraktiointia kytettiin vertailukohtana. Jatkuvatoimisen prosessin optimoinnilla saavutettiin monosakkaridien suurimmaksi tuottavuudeksi 283 mol/(m3 h) (panosprosessille 145 mol/(m3 h). JO-prosessilla saavutettiin korkeat rikki- ja etikkahapon saannot: 97,3 % ja 93,5 %. Monosakkaridisaanto ji hieman alhaisemmaksi (61,7 %) johtuen monosakkaridi- ja rikkihappo-profiilien hankalasta erottamisesta. Ulostulo virtojen puhtaudet olivat korkeat: 89 % monosakkarideille, 89 % rikkihapolle ja 100 % etikkahapolle.
Resumo:
Asthma and allergy are common diseases and their prevalence is increasing. One of the hypotheses that explains this trend is exposure to inhalable chemicals such as traffi c-related air pollution. Epidemiological research supports this theory, as a correlation between environmental chemicals and allergic respiratory diseases has been found. In addition to ambient airborne particles, one may be exposed to engineered nanosized materials that are actively produced due to their favorable physico-chemical properties compared to their bulk size counterparts. On the cellular level, improper activity of T helper (Th) cells has been connected to allergic reactions. Th cells can differentiate into functionally different effector subsets, which are identifi ed according to their characteristic cytokine profi les resulting in specifi c ability to communicate with other cells. Th2 cells activate humoral immunity and stimulate eradication of extracellular pathogens. However, persistent predominance of Th2 cells is involved in a development of number of allergic diseases. The cytokine environment at the time of antigen recognition is the major factor determining the polarization of a nave Th cell. Th2 cell differentiation is initiated by IL4, which signals via transcription factor STAT6. Although the importance of this pathway has been evaluated in the mouse studies, the signaling components involved have been largely unknown. The aim of this thesis was to identify molecules, which are under the control of IL4 and STAT6 in Th cells. This was done by using system-level analysis of STAT6 target genes at genome, mRNA and protein level resulting in identifi cation of various genes previously not connected to Th2 cell phenotype acquisition. In the study, STAT6-mediated primary and secondary target genes were dissection from each other and a detailed transcriptional kinetics of Th2 cell polarization of nave human CD4+ T cells was collected. Integration of these data revealed the hierarchy of molecular events that mediates the differentiation towards Th2 cell phenotype. In addition, the results highlighted the importance of exploiting proteomics tools to complement the studies on STAT6 target genes identifi ed through transcriptional profi ling. In the last subproject, the effects of the exposure with ZnO and TiO2 nanoparticles was analyzed in Jurkat T cell line and in primary human monocyte-derived macrophages and dendritic cells to evaluate their toxicity and potential to cause infl ammation. Identifi cation of ZnO-derived gene expression showed that the same nanoparticles may elicit markedly distinctive responses in different cell types, thus underscoring the need for unbiased profi ling of target genes and pathways affected. The results gave additional proof that the cellular response to nanosized ZnO is due to leached Zn2+ ions. The approach used in ZnO and TiO2 nanoparticle study demonstrated the value of assessing nanoparticle responses through a toxicogenomics approach. The increased knowledge of Th2 cell signaling will hopefully reveal new therapeutic nodes and eventually improve our possibilities to prevent and tackle allergic infl ammatory diseases.
Resumo:
Kelatoivat ioninvaihtimet ovat yleens makrohuokoisia hartseja, joiden avulla metalleja poistetaan ja otetaan mahdollisesti talteen teollisuuden puhdistettavista jtevirroista. Ne muodostavat metalli-ionien kanssa komplekseja runkomateriaaliin kovalenttisesti liitettyjen aktiivisten funktionaalisten ryhmiens vlityksell. Ioninvaihtimen selektiivisyys eri metalli-ioneja kohtaan vaihtelee riippuen siihen liitetyst kelatoivasta ryhmst. Tyss tutkitaan metallien tarttumista kelatoiviin ioninvaihtimiin, sek niiden eluoitumista adsorbentistaan. Kelatoivat ioninvaihtimet sitovat metalli-ioneja tehokkaasti ligandiensa monihampaisuudesta johtuen. Metallien tarttuminen kelatoivaan ioninvaihtimeen ei kuitenkaan ole yksiselitteist, vaan siihen vaikuttaa muun muassa pH yhdess monen muun tekijn kanssa. Ioninvaihtimien selektiivisyytt tarkastellaan tyss lhinn kovien ja pehmeiden happojen ja emsten HSAB -teorian nkkulmasta. Regeneroinnilla ioninvaihdin saadaan jlleen alkuperiseen muotoonsa, mink jlkeen se voidaan kytt uudelleen. Yleens regenerointi suoritetaan kemiallisesti. Tss tyss ioninvaihtimien regenerointia ja kohdemetallin eluointia tarkastellaan paitsi teoriassa, mys kokeellisessa osuudessa. Kokeellisessa osuudessa tutkitaan kuparin (Cu2+) eluoitumista kelatoivasta Dowex M-4195 kationinvaihtohartsista. Kokeissa hartsi ladattiin kuparilla erillisess panoksessa kuparin ollessa syttliuoksessa kuparisulfaattina. Eluointiliuoksina kytettiin 2 ja 5 molaarista rikkihappoa, sek 2 molaarista ammoniumhydroksidia. Eluointi suoritettiin panostoimisena kolonniajona ja eluaatista otetut nytteet analysoitiin atomiadsorptiospektrofotometrill. Analyysitulokset esitetn lpisykyrin, joiden perusteella 2M ammoniumhydroksidi on kolmesta tutkitusta eluentista tehokkain eluoimaan kuparia Dowex M-4195 hartsista.
Resumo:
Abstract: Fifty-five bursa of Fabricius (BF) were evaluated by optical microscopy for three different avian histopathologists (H1, H3 and H4) to determine the degree of lymphoid depletion. One histologist evaluated the same slides at two different times (H1 and H2) with four-months interval between the observations. The same BFs were evaluated using the system of Digital Lymphocyte Depletion Evaluation (ADDL), being performed by three differents operators of the system, not histopathologists. The results showed was a significant difference between the histopathologists and between the scores established by the same expert (H1 and H2). However, there were not significant differences between the scores with the ADDL system, obtained using ADDL. The results make clear the fragility of the subjective lymphocyte depletion score classification by the traditional histologic method, while the ADDL system proves to be more appropriated for the assessment of the lymphoid loss in the BF.
Resumo:
Atrazine persistence in soils of the southeast of Buenos Aires Province, was studied by an oat bioassay. Atrazine doses of 0.58, 1.16, and 2.32 mg.g-1 dry soil weight (DSW) were applied to pots containing soils from Balcaree, A. Gonzles Chaves and San Cayetano sites, whose organic matter (OM) content of soils were 5.70, 5.15, and 3,84%, respectively. Avena sativa cv. Millauqun plants were grownth in the pots under greenhouse conditions at different times after atrazine application. Shoots were evenly cut above the soil and dry weight determined as a measure of plant growth. Plants grown in non-sprayed soil were used as controls. Relative dry weight (RDW) of shoots was calculated as percentage of control. Atrazine phytotoxicity was expressed in terms of 50 % plant growth reduction (GR50) in the soils under study. Herbicide persistence was expressed in terms of days after treatment (DAT) needed for the plant to achieve 80% of RDW. Atrazine GR50 values of 0.30, 0.64, and 0.90 mg.g-1 DSW in soils from San Cayetano, Balcare and A.G. Chaves, were respectively obtained at 42 DAT. Herbicide persistences at the recommended dose (1.16 mg.g-1) were 100, 143, and 221 DAT for A.G. Chaves, Balcarce and San Cayetano soils, respectively. San Cayetano soil had both the lowest OM content and cation exchange capacity (CEC), as well as the highest pH, of all the soil studied here. These results were consistent with both the lowest GR50 and the highest persistence abtained for atrazine in this soil.
Resumo:
Lignocellulosic biomasses (e.g., wood and straws) are a potential renewable source for the production of a wide variety of chemicals that could be used to replace those currently produced by petrochemical industry. This would lead to lower greenhouse gas emissions and waste amounts, and to economical savings. There are many possible pathways available for the manufacturing of chemicals from lignocellulosic biomasses. One option is to hydrolyze the cellulose and hemicelluloses of these biomasses into monosaccharides using concentrated sulfuric acid as catalyst. This process is an efficient method for producing monosaccharides which are valuable platforn chemicals. Also other valuable products are formed in the hydrolysis. Unfortunately, the concentrated acid hydrolysis has been deemed unfeasible mainly due to high chemical consumption resulting from the need to remove sulfuric acid from the obtained hydrolysates prior to the downstream processing of the monosaccharides. Traditionally, this has been done by neutralization with lime. This, however, results in high chemical consumption. In addition, the by-products formed in the hydrolysis are not removed and may, thus, hinder the monosaccharide processing. In order to improve the feasibility of the concentrated acid hydrolysis, the chemical consumption should be decreased by recycling of sulfuric acid without neutralization. Furthermore, the monosaccharides and the other products formed in the hydrolysis should be recovered selectively for efficient downstream processing. The selective recovery of the hydrolysis by-products would have additional economical benefits on the process due to their high value. In this work, the use of chromatographic fractionation for the recycling of sulfuric acid and the selective recovery of the main components from the hydrolysates formed in the concentrated acid hydrolysis was investigated. Chromatographic fractionation based on the electrolyte exclusion with gel type strong acid cation exchange resins in acid (H+) form as a stationary phase was studied. A systematic experimental and model-based study regarding the separation task at hand was conducted. The phenomena affecting the separation were determined and their effects elucidated. Mathematical models that take accurately into account these phenomena were derived and used in the simulation of the fractionation process. The main components of the concentrated acid hydrolysates (sulfuric acid, monosaccharides, and acetic acid) were included into this model. Performance of the fractionation process was investigated experimentally and by simulations. Use of different process options was also studied. Sulfuric acid was found to have a significant co-operative effect on the sorption of the other components. This brings about interesting and beneficial effects in the column operations. It is especially beneficial for the separation of sulfuric acid and the monosaccharides. Two different approaches for the modelling of the sorption equilibria were investigated in this work: a simple empirical approach and a thermodynamically consistent approach (the Adsorbed Solution theory). Accurate modelling of the phenomena observed in this work was found to be possible using the simple empirical models. The use of the Adsorbed Solution theory is complicated by the nature of the theory and the complexity of the studied system. In addition to the sorption models, a dynamic column model that takes into account the volume changes of the gel type resins as changing resin bed porosity was also derived. Using the chromatography, all the main components of the hydrolysates can be recovered selectively, and the sulfuric acid consumption of the hydrolysis process can be lowered considerably. Investigation of the performance of the chromatographic fractionation showed that the highest separation efficiency in this separation task is obtained with a gel type resin with a high crosslinking degree (8 wt. %); especially when the hydrolysates contain high amounts of acetic acid. In addition, the concentrated acid hydrolysis should be done with as low sulfuric acid concentration as possible to obtain good separation performance. The column loading and flow rate also have large effects on the performance. In this work, it was demonstrated that when recycling of the fractions obtained in the chromatographic fractionation are recycled to preceding unit operations these unit operations should included in the performance evaluation of the fractionation. When this was done, the separation performance and the feasibility of the concentrated acid hydrolysis process were found to improve considerably. Use of multi-column chromatographic fractionation processes, the Japan Organo process and the Multi-Column Recycling Chromatography process, was also investigated. In the studied case, neither of these processes could compete with the single-column batch process in the productivity. However, due to internal recycling steps, the Multi-Column Recycling Chromatography was found to be superior to the batch process when the product yield and the eluent consumption were taken into account.
