Fedmis Pty (Ltd) situated in Palaborwa, South Africa produces phosphoric acid using the wet process production process. For this study, two main areas of concern in the wet process phosphoric acid production were investigated. The first area is the formation of sludge in the system due to impurities that reduces the grade of the acid produced, thereby lowering the selling price. The second area is the crystallisation of the gypsum that influences filtration and thereby affects plant productivity. These two aspects were investigated separately as they occur in different steps of the production process at different acid concentrations. A major component of the acid sludge is known as x-compound, ((Fe,Al)3KH)14 (PO4)8.4H2O). The purpose of the investigation of x-compound is to determine what effects different ionic impurities have on its precipitation and to determine if these effects could be used to decrease the amount of sludge formation. Due to the complexity of the system and the wide variety of impurities only the major impurities were considered in this study. These impurities included potassium (K+), sodium (Na+), magnesium (Mg2+), aluminium (Al3+) and iron (Fe3+). For all the experiments investigating the effect of impurities, analytical reagents were used on laboratory scale. For the silica experiments, commercially available samples were used. For the experiments investigating the impurity effects on the precipitation of x-compound it was found that: <ul> <li> Agitation increases x-compound precipitation and can be used commercially to increase the precipitation rate to a point where sludge can be removed before transportation.</li> <li> Adding x-compound seeding crystals or magnesium ions also increases precipitation.</li> <li> Adding gypsum, sodium, hexafluorosilicates or fluorosilic acid reduces the precipitation, with sodium ions producing the lowest yield. This reduction is however not sufficient to be used commercially.</li> </ul> From the Raman study it became clear why x-compound precipitation is such a slow process. E At low acid concentrations, more H2PO4 - ions are present that form a complex with iron and aluminium. E As the acid concentration increases the concentration of H2PO4- ions decrease as the degree of dissociation of phosphoric acid decreases. The ferric- H2PO4- and aluminium- H2PO4- complexes become less stable and ultimately precipitation of the x-compound is favoured above solvation. E Addition of potassium impurities to the solutions had no visible effect on the Raman spectra and is suspected not to form a complex with the acid. From the silica sources investigated namely Dicalite, Serina Kaolin, Foskor silica and Aerosil 200 it can be concluded that none of the sources will be useful for the removal of potassium through formation of potassium hexafluorosilicates. For the determination of the concentration of impurities present in the production of phosphoric acid, the Fedmis monitoring program was initiated. It included the monitoring of Foskor rock analyses on a daily basis, and the monitoring of the 27%, 39% and 54% P2O5 phosphoric acid and precipitate, from these acid solutions on a weekly basis. From the investigation of the effect of these impurities on the solubility of potassium hexafluorosilicates, it was found that magnesium causes K2SiF6 to be the most soluble and fluoride the least. Unfortunately, the impurities did not help to reduce the potassium concentrations in the acid to below the required amount for sludge formation. For the calcium sulphate dihydrate surfactant experiments, the purpose of the investigation was to determine whether higher crystallisation qualities could be obtained to improve plant productivity. The investigation was limited to using surfactants with sulphate or phosphate functionalities and experiments were done on laboratory scale using analytical reagents. Atphos E3205, Atpol E3202 and Atpol E1231 are polyethoxylated alkyl phenol phosphate esters that had no visible effect on the crystal structure of the precipitated gypsum, but differences in the crystal sizes were observed. Smaller crystal structures with relatively equal masses compared to reference experiments are an indication of a growth inhibitor and a nucleation promoter as seen with Atphos E3205 and Atpol E3202. Increased crystal sizes were obtained using Atpol E1231. The use of Calsoline Oil caused a wider crystal size distribution in the precipitated crystals as thin and broad crystals with approximately the same length are found. The crystal mass obtained is also approximately the same as that of the reference experiment. Thus, it can be concluded that the surfactant affects the growth of the crystals and not the nucleation. Arlatone 1489, calcium gluconate monohydrate, Dowfax Hydrotrope and Tamol NN 8906 had no visible effect on the structure or size of the precipitated gypsum crystals. With the use of Nansa SS30, drastic effects were seen on the crystallisation of the calcium sulphate as small hexagonal rods were found. With an increase in surfactant concentration, there is a clear decrease in the mass of crystals obtained as well as crystal size. An increase in the crystal size distribution and a decrease in crystal size reduced the filtration rate dramatically. Experiments carried out for 24 hours exhibited the same trends where there is a decrease in yield with an increase in surfactant concentration. Higher yields were however obtained proving that mass transfer barriers were overcome. The results from these experiments again indicate that the surfactant affects crystal growth and nucleation. With the use of Dowfax 3B2 there is definite reduction in yield with an increase in surfactant concentration reaching a minimum at approximately 70% yield. Due to the presence of large amounts of smaller crystals and the almost constant yield obtained compared to the reference experiment, it can be concluded that this surfactant is a growth and not a nucleation inhibitor. As with Nansa SS30, experiments where Empicol LZ/D was used show a continuous decrease in the yield obtained with an increase in the surfactant concentration. At higher concentration of Empicol LZ/D, it seems as if this surfactant changed from a growth promoter to a growth inhibitor because although broad longer crystals are present, there are now also much smaller crystals formed. The crystal size distribution also broadens considerably. Overall, very high yields were obtained using Empimin KSN70 and the observed crystal size distributions were very narrow. The only difference was that the crystals appeared to be more porous or fibrous compared to the reference experiment. It is recommended that the experiments showing promise as crystal habit modifiers like Nansa SS30 and Empicol LZ/D be investigated in more detail as well as combinations of surfactants. Both the areas of concern in the process were investigated successfully. For the sludge formation problem, it is now clear what effects the precipitation of x-compound as well as what affect the impurities and operating conditions have. For the crystallisation of gypsum using surfactants, it was proven that surfactants could be used to affect crystal growth, shape and distribution and in this way influence filtration. / Dissertation (MSc(Chemical Engineering))--University of Pretoria, 2005. / Chemical Engineering / unrestricted

Brewery effluent that had undergone treatment in an anaerobic digester (AD) was used as an alternative water and nutrient source for hydroponic crop production. Brewery effluent was demonstrated to contain sufficient nutrients to support the growth, flowering and fruiting of Lycopersicum escolentum "Moneymaker" tomato crops. The adjustment of the effluent pH with phosphoric acid to between pH 6.0 and 6.5 increased the development of the crops by around 100% compared to crops grown in unaltered effluent. The pH adjusted effluent-grown plants grew to a mean height of 831.4 ± 21.1 mm and a dry biomass weight of 42.34 ± 2.76 g compared to the unaltered pH effluent plants which grew to a height of 410.6 ± 20.5 mm and a weight of 7.65 ± 0.68 g after 49 days. Effluent treatment in high-rate algal ponds (HRAP) was determined to have no positive effect on the nutritional potential of the effluent for Moneymaker production. The effluent-grown plants did not perform as well as plants grown in inorganic-fertilizer and municipal water. Plants grown in effluent grew taller but did not produce significantly more fruit when phosphoric acid (height: 1573.3 ± 50.4 mm, 19.4 ± 1.4 fruit per plant) was compared to nitric acid (height: 1254.1 ± 25.4 mm, 15.6 ± 1.5 fruit per plant) as the pH adjustment over 72 days. Direct and secondary plant stresses from effluent alkalinity, ammonium nutrition, nitrogen limitation, sodium concentrations and heat stress among other factors were probably confounding variables in these trials and require further investigation. Considering the raw effluent composition and manipulating the AD operation is a potential opportunity to improve overall AD performance, reduce chemical inputs in the effluent treatment process, reduce the final effluent alkalinity, and increase available nitrogen content in the final effluent. The anaerobic digester discharging >1000 m³ of nutrient enriched effluent every day is a resource with considerable potential. The benefits of developing this resource can contribute to cost-reduction at the brewery, more efficient water, nutrient and energy management at the brewery, and offer opportunities for job creation and potentially benefit local food security.

Please read the abstract in the front part of this document / Thesis (PhD (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

Les acides phosphoriques chiraux sont des organocatalyseurs très efficaces qui permettent de catalyser une grande variété de réactions asymétriques. Depuis leur développement en 2004, de nombreux acides phosphoriques à chiralité axiale ou à chiralité centrale ont vu le jour. Cependant, aucun exemple d’acides phosphoriques à chiralité planaire n’avait été reporté.Deux nouvelles familles d’acides phosphoriques à chiralité planaire, possédant un motif paracyclophane et un espaceur ferrocénique ou biphénylène, ont été développées au laboratoire. Les propriétés catalytiques de ces nouvelles familles ont été étudiées, notamment dans la réaction de réduction de quinoléines par les esters de Hantzsch. Une bonne activité et des excès énantiomériques allant jusqu’à 92% ont été obtenus. Ces squelettes à motif paracyclophane ont également été exploités pour développer de nouveaux catalyseurs organométalliques chiraux, qui ont été testés dans des réactions de catalyses organométalliques avec des complexes d’or et de rhodium. / Chiral phosphoric acids as organocatalysts have shown high efficiency and versatility in order to catalyze a lot of reactions. Since their development in 2004, a number of chiral phosphoric acids displaying an axial or a central chirality have been synthesized. Nevertheless, there was no example of planar chiral phosphoric acids.We have developed two new families of planar chiral phosphoric acids, based on a paracyclophane scaffold and displaying a ferrocenic or a biphenylene linker. These phosphoric acids have been evaluated, as organocatalysts, in an organocatalytic reaction of quinolines reduction using Hantzsch esters. Good yields and enantiomeric excess up to 92% have been obtained. These new paracyclophane scaffolds have been used to develop chiral organomelallic catalysts, which have been engaged in gold and rhodium complexes catalysis reactions.

Activated carbon is a highly adsorbing material and has various scopes of uses depending on needs. It is used in many industries and applications e.g. to clean industrial wastewater, in medicine, discolor sugar and so on. What makes AC such a good adsorbent is its porous structure which gives it a high surface area.  This report consists of three parts; general information about Activated Carbon (AC) and its characteristics, to give the reader a sufficient background about AC for continuous understanding throughout the report, an experimental investigation in chemical activation of carbon with phosphoric acid as the chemical reagent and sawdust from both Cuban and Swedish Pine tree as precursors, and a second experimental investigation in chemical activation of carbon with Zinc Sulfate as the chemical reagent and sawdust from Cuban Pine tree as the precursor. For the first experimental part as well as for the second the objective is how to best combine the three parameters; acid concentration, impregnation ratio and activation temperature in order to get the best adsorption performance when preparing activated carbon with different precursor specimens and chemical reagents. The experiments with phosphoric acid activation show that treatment with 40% acid concentration at 400 °C produce an activated carbon with good properties for ammonia adsorption and good iodine number. If a 30% phosphoric acid is used for activation, an activation temperature of 500 °C is recommended. With an impregnation ratio of 1, good adsorption was obtained in the activated carbon produced from Swedish pine while using Cuban pine a higher adsorption was obtained with an impregnation ratio of 2. The experiments with Zinc Sulfate activation show that influence of the sulfate concentration (between 10 % and 40 %) and temperature (between 400 °C and 500°C) on the properties for ammonia adsorption in the produced activated carbon was considerable for low impregnation ratio (0.5 and 1). In general, activation conditions of 20% zinc sulfate concentration, 400 °C and impregnation ratio: 1 are enough to produce an activated carbon with good properties for ammonia adsorption. The adsorption of carbon tetrachloride was lower. Activated carbons produced with 10 % zinc sulfate concentration, 0.5 impregnation ratio and 400 °C activation temperature (the mildest studied conditions) show already good iodine number and BET surface area.  The main conclusion from the thesis work is that the optimal conditions vary widely with wanted results. Therefore a suggestion for future work is to narrow the research to fewer variables and more repetition of the samples.

The main purpose for this project was to, by varying the parameters temperature (400 ˚C and 500 ˚C), acid concentration (10%, 25% and 40%), relative impregnation (0.75, 1.35 and 2.0) and impregnation time (1 h, 2 h and 3 h), evaluate which parameters that affect the product. Also, an investigation was made to determine the interaction of the different parameters. This was done by analysing the properties of the AC with gas adsorption of gasoline and ammonia. Liquid adsorption was analysed with iodine number and the yield of the AC was calculated with two different methods. In general an increasing of the temperature and the impregnation time results in a higher iodine number and higher capacity to absorb gasoline in the produced activated carbon. When the conditions were too strong the iodine number and the capacity to absorb gasoline decreased. The pore structure of the activated carbon is destroyed by too strong conditions. The results were also analysed with a computer program to establish statistical evidence of influence from the parameters indicating that temperature has strong effect on iodine number of the produced activated carbon. If the AC from Caribbean Pine would be commercially produced the recommended design is to keep all parameters low. This is both cost effective and energy efficient. Based on the experimental results it was determined that the AC from Caribbean Pine is better suited for adsorbing gasoline compared with ammonia. Furthermore, the adsorption of gasoline is increasing with an increasing temperature. An industrial manufactured AC was compared with the AC produced from Caribbean Pine and it had a better liquid and gas adsorption showing that more research and optimization of AC from Caribbean Pine must be done before commercializing the product. A suggestion for further research is to use the time in the oven as a parameter to be varied in the experimental setup. This could be valuable in order to determine the influence of the time in the oven both concerning the yield but also the adsorption ability of the AC.

No description available.

This project presents a study of iron technology in Early Medieval (fifth to eleventh centuries AD) Britain through the examination of iron found in settlement contexts. This is a period characterized by significant cultural, political and social changes. The effect of these changes on iron technology has never been investigated on a large scale. Previous studies on iron focused either on individual sites or on single artefact types, and did not provide any clear multi-region interpretive framework. A longstanding problem has been in identifying the extent of usage of a key alloy: phosphoric iron. This research project examined iron assemblages from eight settlement sites of varying size, culture, economic and social status from across Britain. From each settlement a mixed assemblage of iron artefacts was sampled, including edged tools, items of personal adornment, construction materials, and craft tools. Analysis was by traditional archaeometallurgical techniques alongside SEM-EDS elemental analysis. Alloy usage, specifically relating to phosphoric iron, was examined and the manufacturing techniques assessed. It was shown that elemental analysis is the only reliable method to determine the presence of phosphorus in iron and demonstrated that the traditional phosphoric indicators as observed during optical microscopy are insufficient. Results were subjected to a series of comparisons based on settlement size, the inferred social status, and cultural affinities. The results demonstrate the high technological level of iron artefact production across the country. All areas had access to the full range of iron alloys and employed a highly developed range of smithing techniques. Phosphoric iron was a prevalent alloy in this period. Based on these results, a model of the Early Medieval iron industry is generated, suggesting a vibrant economy in which both local and traded irons were significant. / The accompanying data files and image files are not available online.

No description available.

No description available.