Dissertations / Theses on the topic 'Carbonyl sulphide'

The common industrial practice of using aqueous solutions of diethanolamine (DEA) for the removal of impurities such as carbon dioxide (CO₂), hydrogen sulphide (H₂S), carbonyl sulphide (COS) and carbon disulphide (CS₂) from natural, refinery and manufactured gases often entails irreversible reactions between the solvent and the impurities. This phenomenon is referred to as amine degradation and it not only constitutes a loss of the amine but may contribute to operational problems such as foaming, corrosion and fouling. Degradation of DEA by COS and CS₂ was studied by using a 600 mL stainless steel reactor under the following conditions: DEA concentration 10 - 40 wt%; temperature 120 - 195 °C; COS partial pressure 345 - 1172 kPa; CS₂ volume 2.5 - 10.5 mL (CS₂/DEA mole ratio of 0.055 - 0.233). An analytical procedure consisting of gas chromatography (GC) and gas chromatography/mass spectroscopy (GC/MS) was used to identify over 20 compounds in the partially degraded DEA solutions. The major degradation products are monoethanolamine (MEA), bis hydroxyethyl ethylenediamine (BHEED), bis hydroxyethyl piperazine (BHEP), hydroxyethyl oxazolidone (HEOD), hydroxyethyl imidazolidone (HEI), tris hydroxyethyl ethylenediamine (THEED) and bis hydroxyethyl imidazolidone (BHEI); as well as a dithiocarbamate salt (in the case of the CS₂-DEA systems). In addition, both COS and CS₂ induced degradation formed solid products which were characterized on the basis of solubility, melting point, elemental composition, solid probe GC/MS and infrared analysis. The number of degradation compounds in the COS-DEA and CS₂-DEA systems is large when compared with the three major degradation compounds found in CO₂-DEA systems; this demonstrates that the former systems are distinct and more complicated than the latter system. When COS or CS₂ was contacted with aqueous DEA solution, hydrolysis occurred and H₂S, CO₂, COS and, possibly, CS₂ together with their related ionic species were present in the system. Solubility and hydrolysis experiments were therefore conducted to establish the equilibrium composition of the COS-DEA system prior to the commencement of degradation. A modified Kent-Eisenberg (K/E) model which was developed to correlate the experimental data, showed good agreement between the experimental results and model predictions. Since the K/E and previous models were limited to amine-CO₂ and/or H₂S systems, the present modified K/E model which incorporates COS, is a significant improvement. The rate of degradation of DEA was found to increase with temperature, DEA concentration, COS partial pressure and CS₂ volume. On the basis of the experiments conducted to evaluate the contributions of the various compounds in the partially degraded solutions, reaction schemes were developed for the formation of 18 degradation compounds in the COS-DEA and CS₂-DEA systems. Despite the complexity of the reactions, the overall degradation of DEA was well represented by a first order reaction for the present experimental conditions. A mathematical model based on the major reaction schemes was developed to estimate the concentrations of DEA and the major degradation compounds in the COS-DEA system. Contrary to literature information, experiments conducted with gas mixtures of CO₂ and showed that H₂S enhanced the rate of DEA degradation. A direct result of the combined effects of H₂S and CO₂ on alkanolamines was the production of the corresponding lower order alkanolamines from higher order ones. The resulting mixed amine solution increases the routes for degradation compared to single amine solutions. The study therefore provides an indication of what to expect in terms of degradation when mixtures of alkanolamines are used for gas sweetening.
Applied Science, Faculty of
Chemical and Biological Engineering, Department of
Graduate

This thesis presents an investigation of carbonyl sulphide as a new fumigant and related methodology studies. The first part involved the investigation of a new fumigant - carbonyl sulphide, which has the potential to replace methyl bromide. Its biological response or activity was investigated, e.g. toxicity to target organisms and phytotoxicity, environmental and worker safety considerations. In the second investigation, analytical methods were developed for the determination of fumigant movement through timber and fumigant residues in grains as well as a method of chemical fractionation to determine the fate of carbonyl sulphide. A comprehensive literature review of 161 references in these two areas is reported. Carbonyl sulphide was highly toxic to adults of three coleopteran species tested, namely Rhyzopertha dominica (F.), Tribolium confusum du Val, and Sitophilus oryzae (L.), the most sensitive species was R. dominica. For 6 hr exposure at 25�C, the L(CxT)95 value for R. dominica, S. oryzae and T. confusum were, respectively, 36.48, 99.82 and 113.0mg h L-1. Carbonyl sulphide inhibited 100% of mould in wet wheat and more than 90% of mould on dry wheat at lOOmg L-1. Both carbonyl sulphide and hydrogen cyanide were low in phytotoxicity without affecting germination of wheat, at levels needed to control insects. Unlike hydrogen cyanide, carbonyl sulphide can be used at minimum levels without decreasing plumule length of wheat. Chemical data on the sorption of carbonyl sulphide are compared with data from methyl bromide. The levels of carbonyl sulphide in the headspace of five commodities (wheat, barley, paddy, sorghum and peanut) and timbers (hardwood and softwood) decay more slowly than do levels of methyl bromide. Carbonyl sulphide was blown through a column of wheat as easily as was phosphine and more easily than was methyl bromide, and its front was blown out faster than phosphine and methyl bromide. Movement of two fumigants (methyl bromide and carbonyl sulphide) through, and sorption on, softwood and hardwood were studied. Each fumigant was sorbed less on softwood than on hardwood and penetrated softwood better than hardwood. Carbonyl sulphide penetrated timber better than did methyl bromide, and was less sorbed on timber. A rapid method of solvent extraction was developed to enable rapid estimation of the amount on intact fumigant sorbed in wood. This procedure enabled near quantitative recovery of methyl bromide as either intact fumigant or as bromide ion. Carbonyl sulphide residue in unfumigated wheat was found to be around 25- SOppb. Carbonyl sulphide left little residue on fumigated grains. Desorption of carbonyl sulphide from the wheat was extremely fast, 85% of it was released after one day aeration which was very much greater than that of methyl bromide and carbon disulphide. After 6 days aeration the incorporation of 14COS on mungbean, wheat, paddy, rice and safflower was lower than 7Oppb (calculated as COS equivalent). Food value or nutritional quality of foodstuffs is not harmed by carbonyl sulphide fumigation. This result was assessed by identifying any nonreversible change or combined residues in biochemical fractions of commodities including lipids, protein, amino acids, carbohydrate, etc., and no irreversible reaction between carbonyl sulphide and any constituent such as B vitamin, atocopherol, lysine, maltose and starch. Fumigants did not affect lipids, although each fumigant was applied to wheat at exaggerated concentrations, nor wheat germ oil and canola oil treated with extremely high concentration of fumigants. Factors which affect analysis of fumigants including stability of chemicals in extraction solvent and partitioning of fumigant between solvent and air, were examined. The partition ratio, defined as the fumigant concentration in extraction solvent to that in the headspace, varied with fumigant. Methods for multi-fumigant analysis were developed or modified and gave high recoveries and efficiency. The procedure of Daft of solvent extraction followed by partitioning was modified by being performed in sealed flasks. This raised the recovery of carbonyl sulphide, methyl bromide, phosphine and carbon disulphide. Recoveries were near quantitative at levels down to 6-16ppb (w/w) for tested fumigants. Thus the modified Daft method can be adapted to enable determination of the main fumigants used on staple foodstuffs. Microwave irradiation method give higher efficiency of removal of fumigants from grains. Limits of quantification were < 0.2ng g-1 (ppb w/w) for each tested fumigant. The detection limit of COS was calculated, as natural levels of the fumigant were detected in commodities. These are feasible, simple and rapid (< 2 min.) to be use to analyse fumigant residue in grains. Carbonyl sulphide has potential as a fumigant for grain and timber and may replace methyl bromide in some uses, subject to further investigation in commercial situations.

Through the industrial revolution of the last 250 years, trace gases have had a significant impact on the climate. Of particular relevance to this work are species which facilitate the destruction of stratospheric ozone. In this thesis, I focus on four of these species. Understanding the release, reaction and transport pathways of the man-made chlorofluorocarbons (CFCs) could help us to mitigate their destructive effect. Previous studies have found that both source and sink processes significantly alter the isotopic composition of trace gases (e.g. N2O and CFC-12). Measuring these changes can be used to better constrain the interaction of these gases with the atmosphere. Atmospheric histories of δ(37Cl) and δ(13C) in CFC-11, CFC-12 and CFC-113 are presented, covering the last 20 – 60 years. Air samples came from Greenland (NEEM) and Antarctic (Fletcher Promontory) polar firn, with additional samples taken from an archive of Southern Hemispheric background air (Cape Grim, Tasmania). This study extends the novel approach to measuring trace gas isotope ratios in small air volumes (200 – 600 ml), using a single-collector gas chromatography-mass spectrometry system. Carbonyl sulphide (COS) is the principal source of sulphur in the stratosphere, where it breaks down into sulphate aerosol which catalyses the destruction of ozone. Air was extracted from Greenland (NEEM) and Antarctic (DE08, DML (BAS) and DSS) ice core samples and analysed for COS and a range of other trace gas mole fractions. The COS measurements were affected by a previously unknown post-extraction growth effect, leading to higher than expected values. This study also presents new COS measurements in firn air from NEEM and the Southern Hemisphere (EDML, Antarctica). The observed increase and subsequent decrease largely reflects changes in anthropogenic emissions during the 20th century. These measurements also indicate that regional and site-specific effects have a significant influence on the recorded atmospheric history of COS.

The focus of this thesis has been to determine the usable voltage range of carbon-based supercapacitors (SC). Supercapacitors are a relatively new type of capacitors with a vast increase in capacitance compared to capacitors which utilize a dielectric as charge separator. A SC consists of two electrodes and an electrolyte separating the electrodes. The charges are stored by electrostatic forces in the interface between the electrode and the electrolyte, forming the so called electrochemical double-layer (EDL). With porous electrodes the effective surface area of the interfacial zone can be made very large, giving SCs a large storage capacity. The limiting factors of a SC is the decomposition potential of the electrolyte and the decomposition of the electrodes. For commercially manufactured SCs the electrolyte is usually an organic solvent, which has a decomposition potential of up to 2.7-2.8 V. Compared to aqueous electrolytes with a thermodynamic limit of 1.23 V. The drawback of using non-aqueous electrolytes is that they are not environmentally friendly, and they increase the production cost. It is claimed that the voltage range can be up to 1.9 V using aqueous electrolytes. Some researchers have focused on aqueous electrolytes for these reasons. In this thesis two different electrolytes were tested to determine if the voltage range could be extended. The experiments were conducted using a three electrode cell and performing cyclic voltammogram measurements (CV). The carbon electrodes were made of  two different sources of grahite, battery graphite or exfoliated graphite, and nano fibrilated cellulose was added to increase the mechanical stability. The results show that the oxidation potential of the carbon electrode was the positive limit. A usable potential of about 1 V was shown. However, when cycling the electrodes to potentials below the decomposition limit, for hydrogen evolution, interesting effects were seen. A decrease in reaction kinetics, indicating a type of conditioning of the electrode was observed. An increase in charge storage capacitance was also observed when comparing the initial measurements with the final, probably corresponding to an increase in porosity.
KEPS projekt Sundsvall Mitt Universitet

Research goal and objective. To investigate the possibilities of the use of mineral raw materials of local origin for the purification of biogas produced from sewage sludge, by-products and waste and to assess the environmental benefits of the use of biogas in the transport sector. The properties of by-products and waste generated in Lithuania as well as the possibilities of their use in the production of biogas from sewage sludge have been assessed. The potential and properties of local mineral raw materials suitable for the purification of biogas have been assessed. The process of the removal of hydrogen sulphide and carbon dioxide from biogas using natural sorbents has been investigated. It was found that large dolomite resources available in Lithuania allow using this natural raw material for biogas purification because sorbent solutions and suspensions of dolomite powder effectively remove hydrogen sulphide and absorb carbon dioxide from biogas sufficiently quickly. A principal biogas purification technology was developed on the basis of the performed assessment of the process kinetic calculations. Engine perfomance tests were carried out using a mixture of biogas and mineral diesel fuel and exhaust gas emissions were assessed.
Darbo tikslas – ištirti gamtinių sorbentų (vietinės kilmės mineralinių žaliavų) panaudojimo biodujų, pagamintų iš nuotekų dumblo, šalutinių produktų ir atliekų, valymui galimybes bei įvertinti biodujų panaudojimo transporto sektoriuje aplinkosauginę naudą. Įvertintos Lietuvoje susidarančių šalutinių produktų ir atliekų savybės bei panaudojimo biodujų gamyboje iš nuotekų dumblo galimybės. Įvertintos vietinės kilmės mineralinių žaliavų, tinkančių biodujų valymui, potencialas ir savybės. Ištirtas biodujų valymo nuo sieros vandenilio ir anglies dioksido procesas, naudojant gamtinius sorbentus. Nustatyta, kad Lietuvoje eantys dideli dolomito ištekliai leidžia panaudoti šią natūralią žaliavą biodujų valymui, nes absorbciniai tirpalai iš dolomito miltelių efektyviai pašalina sieros vandenilį ir pakankamai gerai sugeria anglies dioksidą. Remiantis atliktu proceso kinetinių skaičiavimų įvertinimu buvo parengta principinė biodujų valymo technologija. Atlikti stendiniai variklio bandymai naudojant biodujų ir mineralinio dyzelino mišinį bei įvertintos deginių emisijos.

Quando as wetlands alcançam a máxima capacidade de tratamento para remover metais pesados, a remoção ainda pode ocorrer por precipitação na forma de sulfetos devido a redução biológica de sulfato. Para alcançar este objetivo, devem ser promovidas condições anaeróbias, uma fonte de sulfato deve existir e uma fonte adequada de carbono/energia deve estar presente. No presente trabalho, a macroalga Sargassum filipendula e bagaço de cana-de-açúcar (materiais lígneo-celulósicos) foram selecionados como fontes de carbono, devido ao seu acentuado conteúdo de compostos orgânicos de degradação lenta e serem resíduos de alta disponibilidade. Experimentos foram simultaneamente conduzidos em operação contínua em duas colunas (0,5 L cada), uma contendo a macroalga e/ou bagaço de cana-de-açúcar e a outra contendo os materiais inoculados com um lodo anaeróbio. Neste trabalho, foi estudada a remoção de cádmio e zinco, devido à presença deles em efluentes de operações de mineração/metalurgia. Os ensaios foram realizados sob três diferentes condições experimentais no que se refere à quantidade de lodo anaeróbio inoculado no reator e o material empregado como fonte de carbono/energia. Os resultados indicaram que o reator inoculado foi capaz de tratar o efluente mais eficientemente que o reator não inoculado, considerando o período dos testes
When wetlands reach maximum treatment capacity to remove heavy metals, removal can still take place through precipitation as sulphides, due to biological reduction of sulphate. To achieve this goal, anaerobic conditions must be attained, a sulphate source must exist, and an adequate carbon/energy source must be present. In the present work, the seaweed Sargassum filipendula and sugarcane bagasse (ligneous-cellulosic materials) have been selected as carbon sources, due to their high content of slow degradation organic compounds and high availability as waste materials. Experiments were simultaneously conducted in continuous operation in two columns (0.5 L each), one containing the seaweed and/or sugarcane bagasse and another containing the materials inoculated with an anaerobic sludge. In this work, the removal of cadmium and zinc was studied, due to their presence in effluents from mining/metallurgy operations. The rehearsals were accomplished under three different experimental conditions in what refers to the amount of anaerobic mud inoculated in the reactor and employed material as carbon/energy source. The results obtained indicated that the inoculated reactor was able to treat the effluent more efficiently than the non inoculated reactor, considering the time-course of the tests

Increasing freshwater scarcity across the world means that wastewater reclamation is being considered as a key method in which to meet the growing demand. Evolution of water reuse schemes where high quality product is required such as for indirect potable reuse has led to the adoption in recent years of the integrated membrane scheme using a combination of microfiltration or ultrafiltration with reverse osmosis membrane. However, despite technological advancements, these membranes are still prone to fouling resulting in increased costs through cleaning or replacement. This thesis aims to look at pretreatment to reduce the fouling propensity of the microfiltration membranes via a 600m3 /d pilot plant which was commissioned to investigate indirect potable reuse. A range of pretreatments including pre-screening, pre-coagulation, powdered activated carbon and granular activated carbon were assessed based on fouling amelioration, water quality improvement and cost analysis. Results showed that ferric sulphate dosing was the most effective in terms of reducing the reversible fouling rate especially at high turbidity loads enabling higher flux to be realised leading to a small cost benefit. Activated carbon proved the most effective pretreatment in terms of organic removal and a significant reduction in the irreversible fouling rate. However, the cost involved in using this as a pretreatment is significant compared to possible cost savings through reduced requirement for chemical cleaning. This pretreatment is only viable if it obviates the need for a separate organic removal process.

Abstract Pollutant (such as metals and sulphate) contamination exists in the wastewaters of many industries, including mining operations, metal plating facilities, and tanneries. Adsorption is one of the most commonly used processes for the removal of pollutants from waters and wastewaters due to its high efficiency and simple operation. Activated carbon is the most frequently used adsorbent material, although its high cost inhibits its widespread use in wastewater treatment. Therefore, there is a need to develop other adsorbents from alternative inexpensive raw materials such as locally available industrial and mineral waste and by-products. The aim of this thesis was to study the possibility of using industrial waste materials such as carbon residue, metakaolin, blast-furnace slag and analcime as an inexpensive sorbent for iron, copper, nickel, arsenic, antimony and sulphate removal from aqueous solutions. To enhance their adsorption capacity, different chemical treatments (i.e. activation, modification, geopolymerisation) were performed. As a result, the level of removal of iron, copper and nickel by carbon residue and zinc chloride activated carbon residue was higher than that by the commercial activated carbon. Iron chloride modified carbon residue was the most effective sorbent material for sulphate removal when compared to the other studied chemically modified/activated carbon residues. Blast-furnace slag and metakaolin geopolymers as well as their raw materials, were examined for the simultaneous removal of nickel, arsenic and antimony from the spiked mine effluent. In the case of blast-furnace slag, geopolymerisation clearly increased the efficiency of nickel, arsenic and antimony removal to a beneficial level. The barium chloride modified blast-furnace-slag geopolymer was a very efficient sorbent material for sulphate removal and it could thus be a technically feasible sulphate sorbent for wastewater treatment (e.g. in the mining industry in applications in which very low sulphate levels are desired). Barium chloride modified acid washed analcime could also be a potential sorbent for sulphate removal
Tiivistelmä Teollisuuden jätevedet kuten kaivosvedet ja metalliteollisuuden prosessien jätevedet voivat sisältää monenlaisia haitallisia ja jopa myrkyllisiä aineita kuten metalleja ja sulfaattia. Adsorptiota käytetään yleisesti esimerkiksi metallien ja orgaanisten yhdisteiden poistossa vesiliuoksista, koska se on tehokas ja yksinkertainen menetelmä. Aktiivihiili on yleisimmin käytetty adsorbenttimateriaali vedenpuhdituksessa, mutta sen hinta joissain tapauksissa rajoittaa sen käyttöä. Tämän vuoksi on tarvetta kehittää vaihtoehtoisia adsorbenttimateriaaleja edullisista raaka-aineista. Viime vuosien aikana on raportoitu mm. teollisuus- ja mineraalijätteistä, joita voidaan hyödyntää vesien ja jätevesien puhdistuksessa. Tämän työn tavoitteena oli hyödyntää teollisuudesta muodostuvia jätemateriaaleja (hiilijäännös, metakaoliini, masuunikuona ja analsiimi) raudan, kuparin, nikkelin, arseenin, antimonin tai sulfaatin poistossa malli- ja jätevesistä. Materiaaleja käsiteltiin erilaisilla kemikaaleilla (aktivointi, modifiointi tai geopolymerointi), jotta niiden adsorptiotehokkuudet paranisivivat poistettavia aineita kohtaan. Tulokset osoittivat, että raudan, kuparin ja nikkelin poisto oli sekä käsittelemättömällä että sinkkikloridilla aktivoidulla hiilijäännöksellä korkeampi kuin kaupallisella aktiivihiilellä. Arseenin, nikkelin ja antimonin poistoa kaivosvedestä tutkittiin masuunikuona- ja metakaoliinigeopolymeereillä, joista masuunikuonageopolymeeri osoittautui tehokkaimmaksi metallien poistajaksi. Bariumkloridilla modifioitu masuunikuonageopolymeeri puolestaan poisti erittäin tehokkaasti sulfaattia kaivoksen jätevedestä. Rautakloridilla modifioitu hiilijäännös ja happopesty bariumkloridilla modifioitu analsiimi osoittatuivat myös lupaavaksi materiaaliksi sulfaatin poistossa

M.Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology
Corrosion responses of some carbon steels, stainless steel and copper alloys in the presence of a culture of bacteria (referred to as SRB-Sulphate-reducing bacteria) found in industrial heat exchangers, was studied to recommend best alloys under this service condition, with techno-economic consideration. Water from cooling towers in three plants in a petrochemical processing complex were analysed for SRB presence. Two of the water samples showed positive indication of SRB presence. The mixed cultures obtained from plant one were grown in prepared media and incubated at 35 °C for 18 days. Potentiodynamic polarisation studies in anaerobic conditions were done on the selected alloys in aqueous media with and without the grown SRB. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were then used to study the corrosion morphology and corrosion products formation. The voltamograms show higher icorr for alloys under the SRB compared to the control media, indicating the SRB indeed increased the corrosion rates. The surface analysis showed pitting on steel alloy ASTM A106-B. Localised attack to the grain boundaries on a selective area, was seen on ASTM A516-70 dislodging the grains, and intergranular corrosion was seen throughout the exposed area of ASTM A179. Copper alloys showed pitting on ASTM B111 grade C71500 (70-30), and denickelification on ASTM B111 grade C70600 (90-10), and is a good alternative material for use apart from carbon steel alloys, recording a low corrosion rate of 0.05 mm/year. The EDS analysis supported the findings showing higher weight percent of iron and sulphur on surface of the alloys after exposure to the SRB media. This implies that the presence of the sulphur ion indeed increased the corrosion rate. ASTM A516-70 carbon steel was chosen as a suitable alternative material to the stainless steel in this environment. The Tafel plot recorded a corrosion rate of 1.08 mm/year for ASTM A516-70 when exposed to SRB media.

Abstract Gasification is an energy conversion method for the utilisation of biomass for obtaining energy (heat and power). In the gasification process carbon residue is formed as a waste. For improving the cost-effectiveness of the gasification process the utilisation of this waste is important and the present legislation also creates requirements for the utilisation of waste material. Activated carbon is typically used for purification of water, for example, wastewaters as well as gaseous emissions. Consequently, commercial activated carbon is fairly expensive and its preparation is energy consuming. However, this inhibits sometimes its widespread use in wastewater treatment and therefore there is a need to develop cost-effective adsorbents from alternative biomass-based low-cost raw materials to remove harmful substances from aqueous solutions. The first aim of this thesis was to determine physical and chemical properties of carbon residues from wood gasification, and fly ashes from burning processes were used as reference samples. The properties are essential to known when evaluating the potential utilisation applications for unknown carbon residue samples. Properties of carbon residue indicate that it would be suitable adsorbent due to the high carbon content but its activation or modification is needed. The second aim was to modify this industrial carbonaceous by-product by physical and chemical activation and chemical modification methods to maximise the adsorption capacity of material. Based on our results, adsorption properties can be enhanced by using zinc chloride as a chemical activating agent, carbon dioxide as a physical activating agent and ferric chloride in the chemical modification and adsorbents with specific surface areas 285, 590 and 52 m2 g-1 were produced, respectively. The third aim was to test produced adsorbents to anions removal. Chemically activated carbon residue removes phosphate well and physically activated carbon residue removes phosphates and nitrates. Chemically modified carbon residue was observed to be suitable sorbent for sulphate removal. Optimal initial pH and concentration were determined and effect of time was studied and kinetic calculations and isotherm analysis was done for studied adsorbents
Tiivistelmä Kaasutus on tehokas tapa hyödyntää biomassaa sähkön- ja lämmöntuotannossa. Kaasutuksessa muodostuu jätteenä hiilijäännöstä, jonka hyödyntäminen on tärkeää kaasutusprosessin kustannustehokkuuden parantamiseksi. Myös nykyinen lainsäädäntö asettaa vaatimuksia jätemateriaalien hyödyntämiselle. Aktiivihiiltä on tyypillisesti käytetty mm. jäteveden sekä kaasujen puhdistukseen. Aktiivihiili on kuitenkin kallista ja sen valmistaminen on energiaa kuluttava prosessi, mikä rajoittaa sen käyttöä. Tämän vuoksi tarvitaan uutta tietoa myös kustannustehokkaampien adsorbenttien valmistamiseen soveltuvista vaihtoehtoisista biomassapohjaisista raaka-aineista. Tutkimuksen tavoitteena oli aluksi määrittää puun kaasutuksessa muodostuneen hiilijäännöksen fysikaalisia ja kemiallisia ominaisuuksia, joiden tunteminen on tärkeää arvioitaessa soveltuvia hyödyntämiskohteita kyseiselle tuntemattomalle jätemateriaalille. Referenssinäytteinä käytettiin polttolaitoksilla muodostunutta lentotuhkaa. Hiilijäännöksen ominaisuuksien perusteella se voisi olla soveltuva adsorbentti, mutta aktivointi tai modifiointi on välttämätöntä hiilijäännöksen adsorptiokapasiteetin parantamiseksi. Työn toinen tavoite oli parantaa hiilijäännöksen adsorptio-ominaisuuksia fysikaalisesti ja kemiallisesti aktivoimalla tai kemiallisesti modifioimalla. Tulosten perusteella adsorptio-ominaisuuksia voidaan parantaa parhaiten käyttämällä sinkkikloridia kemiallisessa aktivoinnissa, hiilidioksidia fysikaalisessa aktivoinnissa ja rautakloridia kemiallisessa modifioinnissa, jolloin valmistettujen adsorbenttien ominaispinta-alat olivat 285, 590 ja 52 m2 g-1. Työn kolmas tavoite oli tutkia valmistettujen adsorbenttien adsorptiokykyä anionien poistossa laboratoriomittakaavassa. Kemiallisesti aktivoitu hiilijäännös poistaa tehokkaasti fosfaattia, fysikaalisesti aktivoitu fosfaattia ja nitraattia ja kemiallisesti modifioitu hiilijäännös on hyvä sorbentti sulfaatinpoistossa. Adsorptiokokeissa määritettiin optimaalinen alku pH ja alkukonsentraatio ja lisäksi tutkittiin ajan vaikutusta adsorptioon. Tulosten perusteella tehtiin kinetiikkamallinnusta sekä isotermianalyysi

Les dangers potentiels liés à l'augmentation de la teneur en CO2 de l'atmosphère, tels que les changements climatiques ou l'élévation du niveau des mers, ont provoqué un grand intérêt pour la séquestration du gaz carbonique dans les formations géologiques. Le moyen thermodynamiquement le plus sûr pour stocker le carbone est sous la forme de minéraux carbonatés, mais il exige une source de cations divalents qui ne soit pas carbonatée. Les roches basaltiques qui présentent de fortes teneurs en calcium, magnésium et fer peuvent être une de ces sources et la possibilité de former des minéraux carbonatés par injection de CO2 dans les roches basaltiques est en cours d'investigation en Islande et dans d'autres endroits du monde. Dans ce cadre, l'objectif de cette thèse est de contribuer à l'optimisation de la précipitation des carbonates dans les basaltes lors de l'injection de CO2 grâce à une série d'études de terrain et de laboratoire complémentaires. Une étude détaillée de la composition chimique des eaux souterraines au pied du volcan Mont Hekla, dans le sud de l'Islande, a d'abord été menée afin d'évaluer l'évolution chimique des fluides et la mobilité des métaux toxiques lors des interactions entre basalte et fluides riches en CO2. Ces fluides fournissent un analogue naturel pour estimer les conséquences de la séquestration du CO2 dans les basaltes. La teneur de ces fluides en carbone inorganique dissous diminue de 3,88 à 0,746 mmole/kg avec l'augmentation de la mise en solution du basalte tandis que le pH passe de 6,9 à 9,2. Ces observations fournissent une preuve directe du potentiel qu'offre la dissolution du basalte pour séquestrer le CO2. Les concentrations des métaux toxiques dans ces eaux sont faibles et la modélisation des chemins réactionnels suggère que la calcite et les (oxy)hydroxydes de fer piègent ces métaux, suite à l'alcalinisation des fluides induite par la dissolution continue du basalte. On sait que ce sont les cations divalents libérés par la dissolution du verre basaltique qui contrôlent la minéralisation du gaz carbonique dans les basaltes. La vitesse de dissolution du verre basaltique peut être accrue par l'addition de ligands qui se complexent avec Al3+. L'ion SO42- fait partie de ces ligands et l'étude de son impact sur la vitesse de dissolution du verre basaltique a été conduite dans des réacteurs de type 'mixed flow' à 50°C et 3 < pH < 10. .
The potential dangers with increased concentration of CO2 in the atmosphere, such as climate changes and sea level rise, have lead to an interest in CO2 sequestration in geological formations. The thermodynamically most stable way to store carbon is as carbonate minerals. Carbonate mineral formation, however, requires divalent cations originating from a non-carbonate source. One such source is basaltic rocks which contain high concentrations of Ca2+, Mg2+ and Fe2+. The potential for forming carbonate minerals through the injection of CO2 into basalt is under investigation in Iceland and several other places around the world. The aim of this thesis is to help optimize carbonate mineral precipitation in basalts during CO2 injection through a series of related field and laboratory studies. A detailed study of the chemical composition of the groundwater surrounding the Mt. Hekla volcano in south Iceland was performed to assess fluid evolution and toxic metal mobility during CO2-rich fluid basalt interaction. These fluids provide a natural analogue for evaluating the consequences of CO2 sequestration in basalt. The concentration of dissolved inorganic carbon in these groundwaters decreases from 3. 88 to 0. 746 mmol/kg with increasing basalt dissolution while the pH increases from 6. 9 to 9. 2. This observation provides direct evidence of the potential for basalt dissolution to sequester CO2. The concentrations of toxic metals in these waters are low and reaction path modeling suggests that calcite and Fe(III) (oxy)hydroxides scavenge these metals as the fluid phase is neutralized by further basalt dissolution. The rate limiting step for mineralization of CO2 in basalt is thought to be the release of divalent cations to solution through basaltic glass dissolution. .

In der vorliegenden Arbeit sind unterschiedliche Kopplungsstrategien des natürlichen Photosystems I (PSI) aus Cyanobakterium Thermosynechococcus elongatus mit verschiedenen Elektrodenoberflächen sowie Interaktion mit Nanomaterialien und Enzymen bearbeitet worden. Zum einen wurde gezeigt, dass die Immobilisierung des PSI auf modifizierten mehr-wandigen Kohlenstoffnanoröhrchen zur funktionalen Photobiohybridelektrode führt. Dabei wurde das PSI mit der Elektrode elektrisch mit Hilfe eines Redoxproteins, Cytochrom c (cyt c), verknüpft. Das System (PSI-cyt c) wurde auch auf eine dreidimensionale Elektrodenoberfläche des Metaloxids Indiumzinnoxid (eng. ITO) übertragen. Hierbei wurde zusätzlich die TransparenzEigenschaft solcher Oberflächen ausgenutzt. Die Präparation solcher transparenter Elektroden wurde optimiert, um höhere Photoströme zu generieren. Weiterhin wurde eine neue Methode der elektrischen Kontaktierung des PSI mit der Elektrode etabliert. Hierfür wurden Fullerene eingesetzt. Durch erhöhte molekulare Effizienz wurde gezeigt, dass Fullerene effektivere Elektronvermittler zwischen PSI und der Elektrode sind als das cyt c. Zusätzlich wurden im Rahmen dieser Doktorarbeit die photokatalytischen Eigenschaften von PSI mit den biokatalytischen Eigenschaften des Enzyms humane Sulphit Oxidase (hSOx) kombiniert. Hierbei wurde das Enzym als ein alternativer und effizienter Elektronzulieferer für PSI eingesetzt. Ein drittes Protein, das cyt c, fungierte als elektrisches Bindeglied und sicherte die elektrische Kommunikation zwischen den katalytischen Proteinen im System und der Elektrode. Die Komplexität des PSI sowie seine Kommunikation mit anorganischen Nanomaterialien und anderen komplexen Biomolekülen, wie z.B. Enzymen, zeigt ein großes Potential des Einsatzes von PSI-basierter Biohybriden in den Biotechnologien der Zukunft.
In this thesis, different strategies for coupling of the natural complex photosystem I from the cyanobacterium Thermosynechococcus elongatus with different electrode surfaces, and the interaction of PSI with nanomaterials and enzymes has been investigated. First, it was shown that immobilization of PSI on modified multi-walled carbon nanotubes (MWNT) leads to a functional photobiohybrid electrode. Here, PSI has been electrically wired to the electrode via a redox-active protein, cytochrome c (cyt c). The system (PSI-cyt c) has been scaled up to the three-dimensional surface of a metal-oxide, indium tin oxide (ITO). Here, additionally the high transparency property of this material has been exploited. The new preparation procedure of such transparent electrodes has been optimized in order to achieve high pohotocurrents. Furthermore, a new method of electric wiring of the PSI with the electrode has been established. Here, fullerenes have been employed. The high molecular efficiency of such a system proves that fullerenes are more effective wiring agents between the PSI and the electrode as compared to the cyt c. Additionally, in this thesis the photocatalytic property of the PSI has been combined with the biocatalytic property of the enzyme human sulphite oxidase, hSOx. Here, the enzyme has been employed as an alternative electron supplier for PSI. The third protein, cyt c, acted as an electric wiring agent and ensured electric communication between both catalytic proteins of the system and the electrode. The versatility of the PSI as well as its communication with anorganic nanomaterials and biological molecules, e.g. such as enzymes, shows a great potential for use of PSI-based biohybrids in the future biotechnological applications.

CAPES
Atualmente há preocupação da sociedade em relação aos impactos gerados pelas indústrias ao meio ambiente. Para produção de celulose e de papel é usada grande quantidade de água, madeira e produtos químicos, sendo gerado efluente nos diferentes processos produtivos da indústria. A matéria orgânica e a cor do efluente do processo Kraft se devem à presença de moléculas derivadas da lignina que são difíceis de serem removidas ou biodegradadas. Com vistas à remedição deste efluente, o presente trabalho busca avaliar a remoção de cor e matéria orgânica residual de efluente de celulose Kraft pré-tratado biologicamente, usando carvão ativado de casca de coco e argila montmorilonita pelo método de adsorção através de delineamentos experimentais. Para remoção de cor e matéria orgânica foram avaliados os fatores: a) pH do efluente; b) massa do material adsorvente no processo de adsorção e c) temperatura. A capacidade de adsorção de matéria orgânica e cor no carvão ativado e argila montmorilonita foram determinados pelo modelo matemático de Langmuir e Freundlich, por meio de ensaios de construção de isotermas de adsorção em efluente Kraft. O efluente foi caracterizado quanto a DQO, DBO5,20, COT e cor verdadeira antes e depois do tratamento terciário. Para o tratamento do efluente foram empregadas duas temperaturas: 25 e 40°C, seguiu-se planejamento fatorial completo 32 em triplicata com ponto central tendo como variáveis pH (5,0; 6,0 e 7,0) e massa de material adsorvente (0,5; 1,0 e 1,5 g). O planejamento experimental utilizado permitiu obter os melhores resultados com carvão ativado em 40 °C, pH 7,0 e 1,5 g de adsorvente com remoção de: 98% de COT, 83% de DQO, 97% de DBO5,20 e 95% de cor verdadeira e para argila em temperatura de 40 oC, pH 7, e 1,5 g de adsorvente com remoção de: 55% de COT, 50% de DQO, 90% de DBO5,20, e 56% de cor verdadeira. A principal variável responsável pela remoção de cor e matéria orgânica foi a massa de adsorvente seguida do pH. Também foi avaliada a possibilidade de aproveitamento do resíduo obtido a partir do processo de adsorção na incorporação de cinzas de carvão na produção de argamassas com teores de 0,4%, 1,0% e 1,2%; em cimento portland, areia e água com tempos de cura de 7 e 28 dias fazendo testes de resistência à compressão. Para a reutilização da argila foram utilizados 15% de argila do processo de adsorção, 25% de vidro e 60% de argila vermelha, para a confecção de corpos de prova cerâmico à temperatura de 1100 oC a 1150 oC. De modo geral, o processo de tratamento proposto neste trabalho utilizando carvão ativado, demostrou ser boa alternativa comparado com argila montmorilonita para redução de cor e matéria orgânica residual do efluente de processo Kraft, tendo-se em vista a utilização da cinza do carvão utilizado no processo de adsorção como um agregado para formação de argamassas na construção civil e argila utilizada na adsorção como material cerâmico.
Nowadays, there is a concern of society regarding the impacts caused by the industries on the environment. Large amounts of water, wood and chemichal are used to produce cellulose and paper, and contaminated effluents are generated through the various industrial processes associated. The organic matter and the color of the Kraft effluent are due to the presence of lignin-derived molecules that are difficult to be removed or biodegraded. With intent to remediate this effluent, this study aim to evaluate the removal of color and residual organic matter from biologically pretreated Kraft effluent, using activated carbon from coconut shell and montmorillonite clay by adsorption method through experimental designs. For the color and organic matter removal, the following factors were evaluated: a) pH of the effluent; b) the mass of the adsorbent material in the adsorption process and c) temperature. The adsorption capacity of organic matter and color in the activated carbon and in the montmorillonite clay were determined by the mathematical model of Langmuir and Freundlich, by means of isotherm adsorption construction in Kraft effluent.The effluent was characterized by COD, DBO5,20, COT and true color before and after the tertiary treatment. For it treatment two temperatures were employed: 25 °C and 40 °C, followed by a 32 full factorial design with center point in triplicate, using pH (5.0, 6.0 and 7.0) and masses of adsorbent material (0.5, 1.0 and 1.5 g) as variables. The experimental design used showed that the best results with activated carbon are obtained at 40 ° C, pH 7.0 and 1.5 g of adsorbent with removals of 98% of TOC, 83% of COD, 97% of BOD5,25 and 95% of true color. With clay, the best results occurred at temperature of 40 ° C, pH 7, and 1.5 g of adsorbent to remove 55% of COT, 50% of COD, 90% of BOD5,20 and 56% of true color. The main responsible for the removal of color and organic matter was the mass of adsorbent, followed by the pH. It was also evaluated the possibility of using the residue obtained from the adsorption process in the incorporation of carbon ash to produce mortars with levels of 0.4%, 1.0% and 1.2% in Portland cement, sand and water, with curing times of 7 and 28 days, for which compressive strength tests were performed. To reuse the clay, 15% of the clay from the adsorption process was used, together with 25% of glass and 60% of red clay, in order to construct ceramics bodies specimen generated at temperatures from 1100 °C to 1150 °C. The treatment process proposed in this work using activated carbon demonstrated to be, in general, a good alternative compared to montmorillonite clay for the color reduction and residual organic matter removal from Kraft process effluent, while residues from both process can be used as aggregates for mortars and ceramic body production.

The modeling results of current global aerosol models agree, generally within a factor of two, with the measured surface concentrations of black carbon (BC) and sulphate (SF) aerosols in rural areas across the northern continents. However, few models are able to capture the observed seasonal cycle of the Arctic aerosols. In general, the observed seasonality of the Arctic aerosols is determined by complex processes, including transport, emissions and removal processes. In this work, the representations of aerosol deposition processes (i.e., dry deposition, in-cloud and below-cloud scavenging) within the framework of the Canadian Global Air Quality Model – GEM-AQ are first enhanced. Through the enhancements in GEM-AQ, the seasonality of the Arctic BC and SF is reproduced, and the improvement in model performance extends to the rest of the globe as well. Then, the importance of these deposition processes in governing the Arctic BC and SF seasonality is investigated. It is found that the observed seasonality of the Arctic BC and SF is mainly caused by the seasonal changes in aerosol wet scavenging, as well as the seasonal injection of aerosols from surrounding source regions. Being able to reproduce the seasonality of the Arctic BC, the enhanced GEM-AQ allows more accurate assessment of the contributions of anthropogenic sources to the BC abundance in the Arctic air and deposition to the Arctic surface. Simulating results on regional contributions to the Arctic BC show a strong dependence on altitude. The results reinforce the previous finding of Eurasia being the dominant contributor to the surface BC in the Arctic, and suggest a significant contribution from Asian Russia. In addition to the seasonality of the Arctic aerosols, the inter-annual variation in the Arctic BC surface concentration is also investigated. To complement the 3-D GEM-AQ model, the atmospheric backward trajectory analysis, together with estimated BC emissions, is implemented as a computational effective approach to reconstruct BC surface concentrations observed at the Canadian high Arctic station, Alert. Strong correlations are found between the reconstructed and the measured BC in the cold season at Alert between 1990 and 2005, which implies that atmospheric transport and emissions are the major contributors to the observed inter-annual variations and trends in BC. The regional contributions estimated annually from 1990 through 2005 suggest that Eurasia is the major contributor in winter and spring to the near-surface BC level at Alert with a 16-year average contribution of over 85% (specifically 94% in winter and 70% in spring). A decreasing trend in the Eurasian contribution to the Arctic is found in this study, which is mainly due to regional emission reduction. However, the inter-annual variation in the North American contribution shows no clear trend.

Abstract This thesis studies the factors that govern transverse cracking during continuous casting of low carbon, niobium microalloyed and boron microalloyed steels. Crack susceptibility in the thick slab, billet and thin slab casting processes are compared by using typical conditions in laboratory hot ductility tests. There is limited published literature on hot ductility in aluminium-killed and siliconkilled boron microalloyed steels and the proposed mechanisms of failure by transverse cracking are contradictory. Few published papers specifically compare hot ductility behaviour of any steels between thick slab, billet and thin slab continuous casting processes. Thus, the basis of this research is to assess the influence of casting parameters and compositional variations on hot ductility behaviour in low carbon steels, niobium microalloyed steels, aluminium-killed boron microalloyed steels and silicon-killed, boron microalloyed steels. The typical temperature ranges, cooling rate and strain rate conditions of the continuous casting processes were used in reheated and in situ melted hot tensile tests performed on steel specimens. Solidification, transformation and precipitation temperatures were calculated using solubility equations and modelled using the Thermo-CalcTM thermodynamics program. Scanning electron microscopy and transmission electron microscopy were used to determine the modes of failure in the tested specimens. In the low carbon steels, hot ductility was improved by increasing the strain rate; by calcium treatment, which minimises copper sulphide and iron sulphide formation; and by maintaining a nickel to copper ratio of 1:1. It was shown that thin slab casting conditions provided the best hot ductility results for the low carbon steels. All the niobium steels showed poor ductility in the single-phase austenite temperature region, indicating that intergranular precipitation of fine niobium carbonitrides was the cause of the poor ductility. It was shown that the hot ductility was greatly improved by calcium treatment, by decreasing the cooling rate and by increasing the strain rate. Slow iv thin slab and thick slab casting conditions provided the best hot ductility results for the niobium steels. Hot ductility was substantially improved in the aluminium-killed boron steels by increasing the boron to nitrogen ratio from 0.19 to 0.75. The results showed that, at cooling rates generally associated with thick slab, bloom and slow thin slab casting, a boron to nitrogen ratio of ≥0.47 was sufficient to avoid a ductility trough altogether. However, under conditions typically experienced in fast thin slab and billet casting, a boron to nitrogen ratio of 0.75 was required to provide good hot ductility. The mechanism of the ductility improvement with increasing boron to nitrogen ratio was found to be enhanced precipitation of boron nitride, leading to a decrease in nitrogen available for aluminium nitride precipitation. In the silicon-killed boron steels, it was found that the boron to nitrogen ratio had the overriding influence on hot ductility and hence on crack susceptibility. Excellent hot ductility was found for boron to nitrogen ratios above 1. Additionally, analysis of industrial casting data showed that the scrap percentage due to transverse cracking increased significantly at manganese to sulphur ratios below fourteen. An exponential decay relationship between the manganese to sulphur ratio and the average scrap percentage due to transverse cracking was determined as a tool to predict scrap levels in the casting plant.

Dissertação de mestrado, Inovação Química e Regulamentação, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2016
O tratamento biológico de água de drenagem ácida de mina (“Acid Mine Drainage” - AMD) contaminada com sulfato e metais pesados utilizando bactérias sulfato-redutoras (“Sulphate Reducing Bacteria” – SRB) continua a ser foco de grande atenção. O posicionamento desta estratégia como alternativa viável deve-se às suas vantagens do ponto de vista económico e de sustentabilidade ambiental, comparativamente aos métodos químicos clássicos. Eficiente remoção de sulfato, baixa produção de lamas e maior estabilidade dos precipitados de sulfuretos metálicos obtidos em comparação com precipitados de hidróxidos metálicos nos métodos clássicos numa faixa de pH mais ampla tornam o método de tratamento biológico competitivo. Esta abordagem utiliza sulfureto de hidrogénio, gerado biologicamente a parir do sulfato da AMD pelas SRB no processo de aceitação de eletrões durante a oxidação de compostos de carbono, o qual se liga aos metais pesados da AMD precipitando como sulfuretos metálicos. A falta de fontes de carbono/dadores de eletrões na AMD torna necessária adição de compostos orgânicos para uma eficiente redução de sulfato a sulfureto no processo de biorremediação desta água. Esta importância da adição de fontes de carbono/dadores de eletrões nos processos de biorremediação com SRB tem recebido a atenção de muitos investigadores, tendo já sido testados para esse fim vários compostos orgânicos. A maior parte dos produtos investigados foram subprodutos de alimentos agrícolas processados, bem como resíduos orgânicos. No entanto, fontes de carbono bem conhecidas, a maioria das quais compostos orgânicos puros como lactato, etanol, metanol e ácidos gordos voláteis, continuam a ser usados porque produzem melhores resultados em termos de eficiência de redução de sulfato. A limitação de utilizar estas fontes de carbono sintéticas é o seu custo. Na bancada de laboratório são viáveis, mas a sua utilização à escala industrial continua a enfrentar desafios de custo, tornando-se quase impossível de implementar. Além de considerações de custo, há outros fatores críticos na escolha adequada de fonte de fontes de carbono/dadores de eletrões para SRB como disponibilidade, degradabilidade, eficiência em termos de redução de sulfato com pouco ou nenhum poluente associado no efluente de descarga, bem como considerações cinéticas e termodinâmicas para favorecer as SRB na inerente competição com outras bactérias, principalmente as metalogénicas. Tendo em conta todos estes fatores, neste trabalho foram testados como fontes de carbono/dadores de eletrões alternativas para as SRB dois sub-produtos industriais conhecidos por serem ricos em açúcares: um melaço de laranja produzido por evaporação de um licor extraído de cascas de laranja pela uma indústria de processamento de sumo laranja e um melaço de beterraba produzido pela indústria de processamento de açúcar a partir de beterraba. Estes dois melaços foram obtidos, respetivamente, numa fábrica de sumo de laranja no sul de Portugal e numa fábrica de açúcar no sul de Espanha. Tendo em consideração a importância do rácio CQO/[SO42-] no uso de fontes de carbono em processos de biorremediação com SRB e tendo em conta o elevado conteúdo de CQO destes melaços, tinham sido previamente testadas no Laboratório de Tecnologias Ambientais (LTA ) do Centro de Ciências do Mar (CCMAR) da Faculdade de Ciências e Tecnologia da Universidade do Algarve, várias diluições dos mesmos em meio Postgate B sem lactato em reatores em descontínuo tentando-se obter rácios próximos de 1.5, o valor teórico estimado de CQO/[SO42-] do meio Postgate B original (com lactato). As diluições 1:200, entre várias outras testadas, deram melhores resultados na redução de sulfato com ambos os melaços testados. Com base nestes estudos anteriores estabeleceu-se que neste trabalho experimental para avaliar a viabilidade do uso melaço de laranja e melaço de beterraba como fontes de carbono/dadores de eletrões no tratamento de AMD fossem utilizadas diluições 1:200. A utilização de diluições de 1:200 de ambos os melaços em AMD com SRB em reatores em descontínuo, resultou numa eficiente redução de sulfato e simultânea remoção de metais pesados em apenas cerca de 14 dias, chegando-se a concentrações em conformidade com as normas legislativas nacionais para as águas de rega em Portugal (Decreto-Lei nº: 236/98, anexo XVI, 1998). Com estes resultados, a experiencias estenderam-se para sistemas em contínuo com 1 mL/h de fluxo usando dois biorreatores de fluxo ascendente anaeróbios de leito fixo (“upflow anaerobic packed bed” - UAPB), um com melaço de laranja e outro com melaço de beterraba, ambos começando com a mesma diluição (1: 200) de melaço em AMD. Depois de otimizar as condições, aumentando o fornecimento de melaço para uma diluição de 1: 133 em AMD, conseguiu-se uma redução de sulfato eficiente e remoção de metais pesados para concentrações abaixo do limite regulamentado para águas de rega em Portugal (Decreto-Lei n.º: 236/98, anexo XVI, 1998), com um tempo de retenção aproximado de cerca de 13 dias em ambos os biorreatores. Devido à complexidade dos melaços utilizados, analisou-se durante os ensaios de biorremediação a presença de açúcares e ácidos orgânicos. As SRB tiraram proveito em sintrofia de outros membros do consórcio de bactérias que degradaram os compostos de carbono dos melaços em formas mais simples viáveis para a redução biológica de sulfato. Nos reatores em descontínuo e em contínuo alguns açúcares e ácidos orgânicos apareceram, estabilizaram e desapareceram dos meios testados revelando tendências que sugerem estar associados ao crescimento e atividade de SRB. Substratos orgânicos complexos, como o melaço, não são completamente degradados em processos com SRB, como tal geram efluentes com níveis relativamente altos de CQO. Os valores de CQO dos efluentes dos biorreatores de SRB alimentados com melaço de laranja e de beterraba foram tão elevadas como 2284mgO2/L e 3948mgO2/L, respetivamente. Embora não haja limite de CQO definido para águas de irrigação em Portugal, o nível CQO destes efluentes é elevado em comparação com o limite de 150mgO2/L de CQO para descargas de águas residuais. No futuro, já fora do âmbito do presente trabalho, a integração duma coluna de aerificação poderá aperfeiçoar ainda mais os efluentes dos sistemas com SRB testados neste trabalho, reduzindo a CQO para valores toleráveis. Em suma, apesar de tudo, os melaços de laranja e beterraba suportaram o processo de biorremediação de AMD baseado em SRB, tal como indicado pela eficiente redução de sulfato e remoção de metais pesados, com um tempo de retenção aproximado de cerca de 13 dias tanto em reatores em descontínuo como de fluxo contínuo.
The biological method of treating high acidic sulphate and heavy metal contaminated acid mine drainage (AMD) effluents from mining industries using sulphate reducing bacteria (SRB) continue to receive wide attention. This is due to its huge advantages ranging from economical point of view to environmental sustainability, positioning it as an alternative bioremediation strategy over the classical chemical techniques. Efficient sulphate reduction, low sludge production and stability of metal sulphide precipitates in comparison to their hydroxide counter parts over wide range of pH continue to make the biological treatment method competitive. This approach uses biologically generated hydrogen sulphide from the AMD sulphates, reduced by SRB in their process of accepting electrons during the oxidation of organic matter, which precipitates the AMD heavy metals as sulphides. Deficiency of AMD in carbon source/electron donor makes the biological sulphate reduction an electron demanding process. In order to compensate the electron insufficiency of this process, an external organic matter as a carbon source/electron donor needs to be added to achieve efficient sulphate reduction. The importance of carbon sources/electron donors for SRB mediated biological sulphate reduction is very high and for this have received attention from many researchers and several sources have been investigated. Most carbon sources investigated include many agriculturally processed food bi-products as well as organic wastes. However, well known carbon sources, most of which are pure organic compounds like lactate, ethanol, methanol and many other volatile fatty acids (VFA), continue to be used as they deliver better results in terms of sulphate reduction efficiency. The limitation of using these well-known synthetic carbon sources is cost. On the bench, results have been good but scaling up industrially continues to face cost challenges as it becomes almost impossible to implement. Apart from cost considerations, critical in making choice for SRB suitable carbon source/electron donor are factors as availability, degradability, efficiency in terms of sulphate reduction or removal with little or no associated pollutant in discharge effluent as well as kinetic and thermodynamic considerations to envisage any inherent SRB competition with methanogens. Taking into account all these factors, in this work we tested two different types of molasses, an orange molasses produced by an orange juice processing industry through the evaporation of a liquour extracted from orange peels and a beetroot molasses produced by a sugar processing industry, as alternate carbon sources/electron donors for the sulphate reducing bacteria (SRB). This two different molasses were obtained from beetroot and orange juice factories from Southern Spain and Southern Portugal respectively as industrial sub-products known to be rich in sugars. Taking into consideration, the importance of COD/SO42- ratio in the use of organic matter carbon sources for wastewater treatment by SRB and bearing in mind the high COD content of these molasses confirmed in a previous initial characterization at the Laboratory of Environmental Technologies (LET) of the Centre of Marine Sciences (CCMAR) at the Faculty of Science and Technology in the University of Algarve, several dilutions had been tested in batch, each of the molasses diluted in postgate B medium without lactate, trying to obtain COD/SO42- ratios surrounding 1.5 in Postgate B medium. The tested batch dilution of 1:200, amongst several other tested dilutions, gave the best efficient sulphate reduction for both molasses. Based on these previous studies it was established that for this work, experiment to evaluate the feasibility of using the orange and beetroot molasses as carbon sources/electron donors in the treatment of AMD would be performed at 1:200 dilutions. The application of the 1:200 dilutions of both molasses in AMD with SRB in batch tests produced efficient sulphate reduction and simultaneous heavy metals removal in just about 14 days with results in compliance with the national legislative standards for sulphate and heavy metal contaminants for irrigation waters in Portugal (Decree Law no: 236/98, Annex XVI, 1998). With these achieved batch results, we extended our experiments to continuous systems with 1mL/hr flow rate using two upflow anaerobic packed bed (UAPB) bioreactors, one with orange molasses and another with beetroot molasses, both starting with the same dilution (1:200) of molasses in AMD. After optimizing the conditions by increasing the molasses supply for a dilution of 1:133 in AMD, we achieved efficient sulphate reduction and heavy metal removal below standard limit of regulation for irrigation waters in Portugal (Decree Law no: 236/98, Annex XVI, 1998) with an approximate retention time of about 13 days in both bioreactors. Due to the complexity of the used molasses, we analized during the bioremediation assays for the presence of sugars and organic acids. The sulphate reducers took advantage of other members of the bacteria consortia who made the molasses carbon substrates available in simpler forms for the SRB syntrophically. Analyzed batch and continuous system effluent samples showed fashions where the sugars and organic acid appeared in tested media, stabilized and disappeared subsequently suggesting an association with the SRB growth and activity. Complex organic substrates like molasses are not completely utilized by SRB processes and as such generate relatively high COD levels in effluents. The COD in the SRB bioreactor effluents were as high as 2284mgO2/L and 3948mgO2/L for bioreactors fed with orange and beetroot molasses respectively. Although there is no COD limit set for irrigation waters in Portugal, the COD level of this effluents are high compared to COD limit for wastewater discharge at 150mgO2/L. Though outside the scope of this work, in future, integrating an aeration column will further meliorate the effluents of the tested systems, reducing the COD content to bearable values. In summary, after all, the investigated orange and beetroot molasses supported the AMD SRB based bioremediation process, as indicated by the efficient sulphate reduction and heavy metal removal with an approximate retention time of about 13 days in both the batch and the continuous flow systems.

M. Tech. Chemical Engineering.
Discusses the reactive properties of oxalate molecules on the surface of activated carbons (ACs) so that they can bind selectively with base metals. Therefore, the experimental plan covered three main axes of study: Chemical modification of AC adsorbent and characterization, adsorption studies in batch and continuous modes, and adsorption modelling.

The past decade has witnessed dramatic changes in the oil and gas industry with the drilling and production extending into progressively deeper waters and higher operating pressures, therefore making it essential to gain a better understanding of the behaviour of gas hydrate at high pressure conditions. New experimental 3-phase H−LW−V (Hydrate−Liquid Water−Vapour) equilibrium data for nitrogen and H−LW−V (Hydrate−Liquid Water−Vapour) and H−LW−LHC (Hydrate−Liquid Water−Liquid Hydrocarbon) data for ethane and propane simple clathrate hydrates were generated by a reliable fixed-volume, isochoric, step-heating technique. The accuracy and reliability of the experimental measurements are demonstrated by comparing measurements with reliable literature data from different researchers. Additional experimental data up to high pressure (200 MPa when available) for CH4, C2H6, C3H8, i-C4H10, N2, Ar, Kr, Xe, H2S, O2, CO and CO2 clathrates have been gathered from literature. The Valderrama modification of the Patel-Teja (VPT) equation of state combined with non-density-dependent (NDD) mixing rules is used to model the fluid phases with previously reported binary interaction parameters. The hydrate-forming conditions are modelled by the solid solution theory of van der Waals and Platteeuw. Langmuir constants have been calculated by both Kihara potential as well as direct techniques. Model predictions are validated against independent experimental data and a good agreement between predictions and experimental data is observed, supporting the reliability of the developed model.

M. Tech., (Chemical Engineering, Department of Chemical Engineering, Faculty of Engineering and Technology Vaal University of Technology|
The methods used to remove potassium sulphate (K2S04) and other impurities contained within Karbochem finishing plant effluent were investigated. Reverse osmosis was explored for this application. The study was conducted in two steps. The first step focuses mainly on the effluent treatment using BW30 flatsheet as well as BW30-2540 spiral-wound reverse osmosis membranes for the rejection of potassium and sulphate ions. The membranes were supplied by Filmtec. The second step reveals the possible use of potassium sulphate obtained from the brine stream in the fertiliser and fertigation industry by a literature search. Reverse osmosis study was conducted on a laboratory scale unit using flat sheet membranes and also on a pilot plant scale using spiral wound membrane modules. The tests were conducted at a feed pressure of 20 bar(g) with the membrane rejections being 98% and 99.1% on flat sheet membrane, and 96.9% and 99.4% on spiral wound membrane for potassium and sulphates respectively. The results show that both membranes have completely desalinated. Significant reduction in the concentrations of all problematic quality parameters, especially of potassium and the sulphate ions was noted. Granular activated carbon (GAC) bed treatment was recommended for pretreatment of the effluent prior to exposure of the membrane to avoid organic fouling of the membrane. GAC treatment was tested to illustrate its effectiveness to adsorb the COD's.
NRF

PhD (Geography)
Department of Geography and Geo-Information Sciences
Improved access to modern affordable, sustainable and reliable energy supply is fundamental in the development of any economy and in the achievement of sustainable development goals. However, energy as a resource is increasingly and becoming scare in many countries and subsequently expensive, with a substantial impact on the socio-economic progress, especially in any country that lacks the financial, physical, social and human capital to secure its energy supply. Energy can also be produced though the anaerobic fermentation of biological waste, such as animal excrement, which is methane-rich. Fermentation also produces a nutrient-rich digestate. Biogas can be used for domestic purposes, such as cooking and heating. Furthermore, it can be converted into electricity. Biogas technology is of particular significance in rural households, where energy crisis are common. This thesis therefore aimed at developing an adoption and sustainable utilisation framework of biogas as an alternative source of energy for greenhouse gases emission reduction in the Limpopo Province. The sample involved 72 households with biogas digesters, which were purposively sampled and 128 households without digesters, which were randomly selected. The study was based on the primary data that were elicited using open and closed-ended questionnaires. Empirically, the results of this thesis developed a sustainable, simplified, appropriate and comprehensive framework for biogas adoption and utilisation, including an analysis of important factors that could influence the adoption of this desired technology, for cost-effectiveness and sustainability.
NRF