Nesteseosten liukoisuuksien mittaaminen

Diplomityön tarkoituksena on tarkastella isobuteenin dimeroitumisprosessin neste-nestetasapainoja. Tavoitteena on määrittää prosessissa esiintyvien komponenttien väliset neste-nestetasapainot. Työn kirjallisuusosassa on tarkasteltu neste-nestetasapainojen teoriaa. Erityisesti on tarkasteltu mittausmenetelmiä sekä kirjallisuudesta löytyneitä laitteistoja binääristen ja ternääristen systeemien neste-nestetasapainojen määritystä varten. Menetelmät ja laitteistot on esitetty erikseen matalassa ja korkeassa paineessa suoritettaville mittauksille. Lisäksi on tarkasteltu näytteenottoa sekä näytteiden analysointimenetelmiä. Kirjallisuusosassa on myös sivuttu kaasu-neste-nestetasapainojen määritystä, mutta työn varsinainen kohde on neste-nestetasapainojen määritys. Työn kokeellisessa osassa määritettiin iso-oktaaniprosessissa esiintyvien komponenttien välisiä binäärisiä ja ternäärisiä neste-nestetasapainoja. Mitattavien komponenttiparien määrää karsittiin ja jäljellejääneiden parien välillä suoritettavat mittaukset jaoteltiin matalassa ja korkeassa paineessa suoritettaviin määrityksiin. Ternääriset mittaukset tulivat kyseeseen sellaisten komponenttiparien kohdalla, joissa toisiinsa täysin liukenevien nesteiden systeemiin kolmatta komponenttia lisättäessä saatiin aikaiseksi kaksi nestefaasia. Tällaisesta mittaustiedosta voidaan määrittää neste-nestetasapainomallien parametrejä. Mittausten lisäksi kokeellisessa osassa tarkasteltiin näytteenottoa sekä näytteiden analysointia.

Kakun rakenteen vaikutus pesutulokseen

Tässä työssä tutkittiin suodatukseen vaikuttavien tekijöiden vaikutusta suodatuksessa syntyvän kakun ominaisuuksiin sekä kakun ominaisuuksien vaikutusta syrjäytyspesun tehokkuuteen. Lisäksi määritettiin tärkeimmät suodatusparametrit sekä niiden riippuvuudet suodatusolosuhteista. Toissijaisena tavoitteena oli lisäksi tutkia, miten suodatusolosuhteita ja suodatettavan lietteen ominaisuuksia muuttamalla voidaan vaikuttaa suodatusjakson kestoon. Työn kirjallisuusosassa käsiteltiin aluksi yleisesti kiintoaineen erotusta nesteestä. Tämän jälkeen käsiteltiin yleisimmät suodatustekniikat ja tarkasteltiin yksityiskohtaisemmin painesuodatusta ja varsinkin syntyvän kakun rakenteeseen vaikuttavia tekijöitä. Lopuksi käytiin läpi kakulle suodatuksen jälkeen suoritettavat jälkikäsittelymenetelmät ja selvitettiin varsinkin syrjäytyspesun tehokkuuteen vaikuttavia tekijöitä tarkemmin. Kokeellisessa osassa tehtiin koesuodatuksia lietteellä joka sisälsi hienojakoista pigmenttiä. Koesuodatukset tehtiin kahdella eri kankaalla panostoimisella piston press- laboratoriopainesuodattimella johon oli liitetty tiedonkeruuohjelmisto, joka keräsi tiedostoon paineet suodatuskammiossa, kankaan alapuolella ja työsylinterin syöttölinjassa sekä lisäksi männän korkeuden, lietteen lämpötilan ja suodosvaakalukeman. Lietteiden ominaisuuksia seurattiin analysoimalla niiden kiintoainepitoisuuksia, kloridipitoisuuksia, z-potentiaaleja ja partikkelikokojakau-mia siten että jokaisessa suodatuksessa käytetyn lietteen ominaisuudet olivat tiedossa. Suodatusten jälkeen syntyneistä kakuista määritettiin kiintoaine- sekä joissain tapauksissa myös kloridipitoisuudet. Suodatus- ja puristuspaineiden havaittiin vaikuttavan kakkujen huokoisuuksiin ja ominaisvastuksiin selvästi, joskin muutokset olivat melko pieniä. Vaikutus näkyi selvästi myös suodatusten kestoissa ja muutosten havaittiin olevan merkittävän suuruisia. Myös lietteen pH:n havaittiin vaikuttavan merkitsevästi suodatusten kestoihin ja kakkujen ominaisuuksiin. Pesutuloksen ja kakun ominaisuuksien välille löydettiin riippuvuus heikoksi jääneestä pesutuloksesta huolimatta. Myös koesuodatuksissa käytettyjen kankaiden välillä havaittiin selviä eroavaisuuksia.

Modeling of Gold Cyanidation

The chemistry of gold dissolution in alkaline cyanide solution has continually received attention and new rate equations expressing the gold leaching are still developed. The effect of leaching parameters on gold gold cyanidation is studied in this work in order to optimize the leaching process. A gold leaching model, based on the well-known shrinking-core model, is presented in this work. It is proposed that the reaction takes place at the reacting particle surface which is continuously reduced as the reaction proceeds. The model parameters are estimated by comparing experimental data and simulations. The experimental data used in this work was obtained from Ling et al. (1996) and de Andrade Lima and Hodouin (2005). Two different rate equations, where the unreacted amount of gold is considered in one equation, are investigated. In this work, it is presented that the reaction at the surface is the rate controlling step since there is no internal diffusion limitation. The model considering the effect of non-reacting gold shows that the reaction orders are consistent with the experimental observations reported by Ling et al. (1996) and de Andrade Lima and Hodouin (2005). However, it should be noted that the model obtained in this work is based on assumptions of no side reactions, no solid-liquid mass transfer resistances and no effect from temperature.

Sinkkirikasteen liukenemisnopeuteen vaikuttavat tekijät ja sinkkirikasteen suoraliuotuksen mallintaminen

Työn kirjallisuusosassa selvitettiin eri tekijöiden (lämpötila, paine, mineralogia, partikkelikoko, sekoitus, kiintoainepitoisuus, liuoksen happo-, rauta- ja happipitoisuus) vaikutusta sinkkirikasteen suoraliuotusprosessin tärkeimpiin ilmiöihin (diffuusio, aineensiirto, reaktiokinetiikka). Kirjallisuusosassa kartoitettiin myös tämän hetkistä tietämystä niistä tekijöistä, jotka ovat oleellisia, kun sinkkirikasteen suoraliuotusprosessia mallinnetaan. Näitä tekijöitä ovat: sinkkirikasteiden liuotuksen kemia, sinkkirikasteiden liuotuksen kinetiikka ja mekanismit, kaasuneste aineensiirto ja kiinteäneste aineensiirto. Lisäksi selvitettiin millä tavoin aikaisemmissa tutkimuksissa sinkkirikasteiden suoraliuotusta on mallinnettu. Mallinnusosassa käsiteltiin atmosfääristä sinkkirikasteen suoraliuotusta, jossa hapettimena toimi ferri(III)rauta. Mallintamisessa käytettiin kirjallisuudessa esitettyjä mittaustuloksia ja mallintaminen tehtiin Modest tietokoneohjelmistolla. Työssä tehty atmosfäärisen suoraliuotuksen mallintaminen labo-ratoriomittakaavassa (laimeat liuokset ja pienet kiintoainepitoisuudet) antoi lupaavia tuloksia. Ongelmia mallin ennustuksen kanssa esiintyi pienissä happopitoisuuksissa, alhaisissa lämpötiloissa sekä pienillä ja suurilla partikkeleilla. Työn kirjallisuusosassa tunnistettiin ne ongelmakohdat, jotka vaativat lisätutkimuksia, jotta sinkkirikasteen atmosfääriselle suoraliuotukselle pystytään kehittämään simulointimalli. Näitä ovat: 1. Hapen liukoisuus ja aineensiirto teollisuuden käyttämissä sinkkirikastelietteissä, 2. Sopivien mittaustulosten puuttuminen, jotta atmosfääristä suoraliuotusta, jossa O2 ja Fe3+ toimivat hapettimena voitaisiin mallintaa, 3. Kiinteäneste aineensiirron merkitys sinkkirikasteen suoraliuotuksessa. Mallinnusosassa osoitettiin, että mekanistisella mallintamisella voidaan simuloida sinkkirikasteen atmosfääristä suoraliuotusta ainakin laboratoriomittakaavassa. Työn perusteella voidaan todeta, että sinkkirikasteen atmosfääriselle suoraliuotukselle voidaan työssä ehdotettujen jatkotutkimusten avulla kehittää numeerinen mekanistinen malli, jolla atmosfääristä sinkkirikasteiden suoraliuotusprosessia voidaan simuloida eri olosuhteissa.

Gerenciamento de resíduos laboratoriais: recuperação de elementos e preparo para descarte final

This work shows some laboratory waste management developed in order to recover some elements or to prepare the waste for a correct final disposal. The 25 elements chosen cover basically all chemical behaviors found for the metals in the Periodic Table. The treatments adopted were based on the classical behavior in aqueous solution (wet chemistry) but an important condition for a full success was the previous knowledge of the qualitative composition of the wastes treated. Some general trends were found: the final liquid waste was always saline and normally presented a higher volume than the original waste; most original wastes were acid in nature; steps such as solid-liquid separation, washing, evaporating and calcining were currently performed. This work was also a very good experience in chemistry in solution for students and showed them the need of treating wastes for a better environment.

A relevante potencialidade dos centros básicos nitrogenados disponíveis em polímeros inorgânicos e biopolímeros na remoção catiônica

This review reports the application of inorganic and organic polymeric materials for cation removal by using nitrogenated basic centers. The data demonstrate the importance of the desired groups when free or immobilized on natural or synthesized inorganic polymers through silanol groups. Thus, the most studied silica gel is followed by natural crysotile and talc polymers, and the synthesized mesopore silicas, talc-like, silicic acids, phosphates and phyllosilicates. The organic natural biopolymeric chitin and cellulose were chemically modified to improve the availability of the amine groups or the reactivity with desirable molecules to enlarge the content of basic centers. The cation removal takes place at the solid/liquid interface and some interactive effects have their thermodynamic data determined.

The influence of crystallization conditions on the filtration characteristics of sulphathiazole suspensions

Cooling crystallization is one of the most important purification and separation techniques in the chemical and pharmaceutical industry. The product of the cooling crystallization process is always a suspension that contains both the mother liquor and the product crystals, and therefore the first process step following crystallization is usually solid-liquid separation. The properties of the produced crystals, such as their size and shape, can be affected by modifying the conditions during the crystallization process. The filtration characteristics of solid/liquid suspensions, on the other hand, are strongly influenced by the particle properties, as well as the properties of the liquid phase. It is thus obvious that the effect of the changes made to the crystallization parameters can also be seen in the course of the filtration process. Although the relationship between crystallization and filtration is widely recognized, the number of publications where these unit operations have been considered in the same context seems to be surprisingly small. This thesis explores the influence of different crystallization parameters in an unseeded batch cooling crystallization process on the external appearance of the product crystals and on the pressure filtration characteristics of the obtained product suspensions. Crystallization experiments are performed by crystallizing sulphathiazole (C9H9N3O2S2), which is a wellknown antibiotic agent, from different mixtures of water and n-propanol in an unseeded batch crystallizer. The different crystallization parameters that are studied are the composition of the solvent, the cooling rate during the crystallization experiments carried out by using a constant cooling rate throughout the whole batch, the cooling profile, as well as the mixing intensity during the batch. The obtained crystals are characterized by using an automated image analyzer and the crystals are separated from the solvent through constant pressure batch filtration experiments. Separation characteristics of the suspensions are described by means of average specific cake resistance and average filter cake porosity, and the compressibilities of the cakes are also determined. The results show that fairly large differences can be observed between the size and shape of the crystals, and it is also shown experimentally that the changes in the crystal size and shape have a direct impact on the pressure filtration characteristics of the crystal suspensions. The experimental results are utilized to create a procedure that can be used for estimating the filtration characteristics of solid-liquid suspensions according to the particle size and shape data obtained by image analysis. Multilinear partial least squares regression (N-PLS) models are created between the filtration parameters and the particle size and shape data, and the results presented in this thesis show that relatively obvious correlations can be detected with the obtained models.

Produção de etanol a partir de torta de mamona (Ricinus communis L.) e avaliação da letalidade da torta hidrolisada para camundongos

The castor bean cake is rich in starch (48 ± 0.53%) and bears a problem linked to the occurrence of a toxic protein (ricin). The chemical hydrolysis (ratio solid:liquid = 1:6; H2SO4= 0.1 mol L-1; 120 °C; 40 min) generated a medium with 27 g L-1 of reducing sugars (hydrolysis efficiency= 32%). The hydrolyzed product was fermented and produced 11 g L-1 of ethanol (volumetric productivity=1.38 g L-1 h-1 and ethanol yield on substrate consumed=0.45 g g-1). In vivo experiments (DL50) revealed a reduction of roughly 240 times in the CBC toxicity (2.11 µg g-1).

Adsorção de íons fosfato em óxido de nióbio hidratado

The adsorption kinetics of phosphate on Nb2O5.nH2O was investigated at initial phosphate concentrations 0.25, 0.50 and 1.00 mg.L-1. The kinetic process was described by a pseudo-second-order rate model very well. The adsorption thermodynamics was carried out at 298, 308, 318, 328 and 338 K. The positive values of both ΔH and ΔS suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption. ΔG values obtained were negative indicating a spontaneous adsorption process. The Langmuir model described the data better than the Freundlich isotherm model. The effective desorption could be achieved using water at pH 12.

Estudo da eficiência de degradação de tetracloreto de carbono por plasma térmico e caracterização dos produtos formados

Decomposition of carbon tetrachloride in a DC thermal plasma reactor was investigated in argon atmosphere. The operational parameters such as plasma torch power and argon flow rate versus CCl4 conversion were examined. The CCl4 net degradation was determined by GC-FID, the chlorine produced was quantified by iodometric titration, the solid carbon was characterised by Raman spectroscopy and by BET analysis. The solid carbon collected inside de plasma reactor was submitted to solid/liquid extraction and the desorbed species were identified by GC-MS.

Recovery of manganese and zinc from spent Zn-C and alkaline batteries in acidic medium

The anode and the internal paste of spent Zn-C and alkaline batteries were leached with 2 mol L-1 H2SO4 at 80 ºC for 2 h. Solid/liquid ratio was 1/10 (g mL-1). The leachate was treated with Na2S in order to precipitate Hg, Cd and Pb. Zn was quantitatively isolated at pH 1,5-2 by adding Na2S. Mn can be precipitated at pH close to 7. Na2S may be replaced by oxalic acid. Zn precipitated at pH around 0, whereas Mn was quantitatively recovered at pH > 4. Acidity control is a critical parameter. Na2SO4 and carbon are the end products.

Aproveitamento da glicerina proveniente da produção de biodiesel na obtenção de híbrido de caulinita para adsorção de Cr3+

The aim of this work was to contribute to the creation of new ways of treating wastewater contaminated with Cr3+, based on solid-liquid adsorption. An adsorbent material was prepared by functionalization of kaolinite with glycerin biodiesel by-product. This material was tested for adsorption performed using a batch method, and results showed that inclusion of glycerin in the structure of kaolinite led to a significant increase in the capacity of Cr3+ adsorption. This contributes to the allocation of by-product of biodiesel and to the treatment of effluents from tanneries.

Otimização, validação e aplicação de método para determinação da concentração residual de difenoconazol em morangos após múltiplas aplicações

Difenoconazole residues in strawberry fruit cultivated in pots were estimated using the solid-liquid extraction with low temperature partition (SLE/LTP) method for sample preparation and gas chromatography with electron capture detection (GC/ECD) for analysis. The optimized method presented excellent recovery values from fortified samples and reproducibility (average recovery values ≥ 98%; CV values < 15%). Linearity of response was demonstrated (r = 0.995) with a detection limit of 9 µg kg-1. The method was successfully applied for the determination of difenoconazole residues in strawberries. Based on these results, the fungicide dissipates quickly, but the residual concentration increases after multiple applications.

Desenvolvimento do método de extração sólido-líquido com partição em baixa temperatura para determinação de inseticidas em grãos de milho ozonizados

The objective of this study was to optimize and validate a solid-liquid extraction method with low-temperature partitioning (SLE/LTP) for the analysis of pesticides. This method was coupled with gas chromatography (GC/ECD) and used to evaluate the degradation of bifenthrin and pirimiphos-methyl in maize grains on exposure to ozone. The optimized SLE/LTP-GC/ECD method is simple, effective and consumes low quantities of the solvent. It can be routinely used for the determination of bifenthrin and pirimiphos-methyl in maize samples. The use of this method of analysis determined that the levels of the insecticides in maize grains were reduced on exposure of the grains to the ozone gas. The observed reduction in the levels of insecticide was directly proportional to the increase in the concentration of the ozone gas.

Otimização e validação da extração sólido-líquido e purificação em baixa temperatura de HPAs em lodo de esgoto

In this study, a method of solid-liquid extraction and purification at low temperature (SLE-PLT) to determine 16 polycyclic aromatic hydrocarbons (PAHs) in sewage sludge was optimized and validated. The analyses were performed by HPLC-UV. The extraction phase, homogenization procedure, influence of pH, ionic strength and clean-up of the extracts were optimized. Recoveries were higher than 63.4% for 11 PAHs. The correlation coefficients were greater than 0.99 and limits of detection and quantitation were less than 0.060 and 0.15 µg g-1, respectively. These values were lower than the maximum residue limits of PAHs established by European legislation. SLE-PLT proved a more practical, economical method with fewer steps compared to Soxhlet extraction (reference method) for PAHs in sewage sludge.