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

No description available.

Foam fractionation is an adsorptive bubble separation technology that has shown potential as a replacement to the more costly and non-sustainable traditional downstream processing methods such as solvent extraction and chromatography for biological systems. However biological systems mostly tend to be a mixture of surface active species that complicates the foam fractionation separation. In this thesis a detailed experimental study on the application of foam fractionation to separate a well-defined surfactant-protein mixture was performed with emphasis on the competitive adsorption behaviour and transport processes of surfactant-protein mixtures in a foam fractionation process. Surface tension and nuclear magnetic resonance (NMR) measurements showed that nonionic surfactant Triton X−100 maximum surface pressure, surface affinity and diffusivity were a factor of 2.05, 67.0 and 19.6 respectively greater than that of BSA. Thus Triton X−100 dominated the surface adsorption at an air-water surface by diffusing to the surface and adsorbing at the surface faster than BSA. This competitive adsorption behaviour was observed in foam fractionation experiments performed for Triton X−100/BSA mixtures for different feed concentration ratios and air flow rates. The recovery and enrichment of Triton X−100 were found to increase and decrease respectively with increasing air flow rate for all foam fractionation experiments as expected for a single component system. However the recovery and enrichment of BSA were both found to increase with increasing air flow rate for high feed concentrations of Triton X−100.Bubble size measurements of the foamate produced from foam fractionation experiments showed that at steady state conditions the bubbles rising from the liquid pool were stabilised by BSA. However at the top of the column the recovery of Triton X−100 in the foamate (75% to 100%) was always greater than the recovery of BSA (13% to 76%) for all foam fractionation experiments. In addition, for high feed concentrations of both components and at low air flow rates, the enrichment of BSA remained at almost unity for most experiments and only increased when the recovery of Triton X−100 reached 100%. Thus it was concluded that Triton X-100 displaced the adsorbed BSA from the surface. The foam drainage properties of Triton X−100/BSA mixtures were characterised using two methods; forced foam drainage and from pressure profiles of steady state foam fractionation experiments (pressure method). The drainage data from the forced foam drainage was found not to be compatible with experimental foam fractionation results, by indicating that stable foam was not produced during the foam fractionation experiments. However stable foam was repeatedly produced during foam fractionation experiments. The drainage data from the pressure method was found to be in close agreement to experimental foam fractionation experiments. The work in this thesis takes a significant step beyond the literature experimental foam fractionation studies for multicomponent systems. In addition to investigating the effect of foam fractionation process parameters on the separation of mixed systems, the results from the characterisation studies of surface adsorption and foam properties provided insight and deeper understanding of the competitive adsorption behaviour of surfactants and proteins in a foam fractionation process.

The interfacial adsorption and bulk properties of a collagenous polypeptide derived from chicken eggshell membranes, the 40 KDa polypeptide, and its mixtures with common low molecular weight (LMW) surfactants, SDS, DTAB and C10E8, have been studied for the first time using surface tension, ζ-potential, foam observations and neutron scattering techniques. The biopolymer has been shown to act as an effective biosurfactant by lowering the surface tension of water below the values commonly achieved with conventional LMW surfactants, i.e. γ = 32 ± 1 mN/m. This capability is maximized at its isoelectric point, pH ~5, and addition of NaCl does not have a major impact upon adsorption. On its own, the 40 KDa polypeptide lacks the ability to foam. When mixed with cationic and anionic surfactants, a positive synergy is observed at low concentrations of both materials that exceeds the expectations from the individual components due to the formation of polypeptide/surfactant complexes with high surface activity and high ability to foam and foam stability. At these concentrations, maximum interfacial adsorption is achieved. The synergy is observed in spite of the type of charges present in the surfactant polar head. However, under the conditions studied, there is a difference in behaviour in regards to colloidal stability and surface film formation between the mixed solutions with the anionic SDS and the cationic DTAB. The non-existence of the synergy in the surface adsorption profile of the mixtures of the polypeptide with the non-ionic surfactant C10E8, as obtained via the plate method, suggests that electrostatic interactions are necessary for this strong synergy to act. ζ-potential has been used to prove the electrostatic nature of the synergy. Specular neutron reflection and SANS measurements offered an insight into the complex size and structure. The 40 KDa polypeptide thus offers a promising alternative to the use of high amounts of LMW surfactants in a range of products in which low surface tension and/or high and stable volumes of foams are needed, by combining small amounts of polypeptide and an ionic surfactant. This could be exploited by industries which have an interest in nanoparticle formation such as personal care or pharmaceutical companies. However, further work is needed to fully characterize these interactions.

Extracting and producing heavy oil presents many difficulties, promoted by the nature of the constant quantities involved, such as viscosity of the oil, the means through where it moves the salinity of water, oil composition, the temperature and so forth. In the pumping, the amount of oil which is drawn is not enough to meet the expenses, that is, the cost-effectiveness has not been satisfactory. This work (Collection and Characterization of Emulsion to the correction of Heavy Oil Flow) sought to analyze the physical and chemical behavior and rheology of emulsions regarding the mobility and displacement of Heavy Oil. With the prior characterization of heavy oil from a study in the wells of the regions and UN-SEAL using sodium dodecyl sulfate (SDS) emulsion type water and oil were obtained (W / O). To the obtainment and the formulation of the oil-water emulsion type, the use of surfactant was essential to the choice of the anionic SDS, since this surfactant is widely used in the petroleum industry. The developments made in this work, in other words, obtaining the w / o emulsions, showed a decrease in viscosity, the shear stress with increasing shear rate with the behavior of a pseudo plastic fluid. It follows that achieving the w / o emulsions, in the micellar concentrations such as 6.67 x 10-2 g.mL-1, 1.0 x 10-1 g.mL-1 and 3.75 g.mL-1 to obtain the w / o emulsions were satisfactory, compared to concentrations of ions present in the oil sample, the pH, the levels of aromatics, resins and asphaltenes, the API gravity, the density, the shaking time, 6 min , the rotation speed of 1000 RPM ± 50, the temperature of 27 ° C, with the breaking time o the emulsion 300 min observed that the viscosity of emulsified oil, tension and shear rate were reduced. Therefore, emulsion water / oil (W / O), obtained in this study achieved the goal of working to reduce the parameters that affect the mobility of heavy oil. / Extrair e produzir óleo pesado apresentam muitas dificuldades, promovidas pela natureza das constantes grandezas envolvidas tais como: viscosidade do óleo, meio por onde este se desloca, a salinidade da água presente no meio, a composição do óleo, a temperatura do meio e outras. No bombeamento a quantidade arrastada de óleo não é bastante para fazer frente aos gastos, isto é, o custo-benefício, não tem sido satisfatório. O presente trabalho (Obtenção e Caracterização de Emulsão para Correção de Escoamento de Óleo Pesado) buscou analisar o comportamento físico-químico e reológico de emulsões quanto à mobilidade e o deslocamento do Óleo Pesado. Com a caracterização prévia do óleo pesado em estudo proveniente de poços da região UN-SEAL e utilizando o Dodecil Sulfato de Sódio (SDS) foram obtidas emulsões tipo Água e Óleo (A/O). Para formulação e obtenção de emulsão tipo água-óleo, o uso de surfactante foi imprescindível. A escolha do aniônico SDS, uma vez que, este surfactante é muito utilizado na indústria do petróleo. Os desenvolvimentos realizados nesse trabalho, ou seja, a obtenção das emulsões A/O, mostrou uma diminuição da viscosidade, da tensão de cisalhamento com o aumento da taxa de cisalhamento com um comportamento de um fluido pseudo-plástico. De onde se conclui que a obtenção das emulsões A/O, nas concentrações micelares tais como: 6,67x 10-2 g.mL-1, 1,0x 10-1g. mL-1 e 3,75 g.mL-1 para a obtenção das emulsões A/O, foram satisfatórias, relativamente às concentrações de íons presentes na amostra de óleo, do pH, dos teores de aromáticos, resinas e asfaltenos, do grau API; da massa especifica,do tempo de agitação, 6 min, a velocidade de rotação 1000±50 RPM, a temperatura do meio 27 ºC, com tempo de quebra da emulsão 300 min observado que a viscosidade do óleo emulsionado, tensão e taxa de cisalhamento foram reduzidas. Portanto, emulsões água/óleo (A/O), obtidas neste estudo atingiram o objetivo do trabalho de reduzir os parâmetros que interferem na mobilidade do óleo pesado.

<p>Savremene svetske tendencije upućuju na sve &scaron;iru primenu<br />ekstrakata lekovitog i aromatičnog bilja, kako u prehrambenim<br />proizvodima&ndash; funkcionalna hrana, tako i u proizvodima<br />farmaceutske i kozmetičke industrije. Ekstrakti biljnog<br />materijala, dobijeni primenom ugljendioksida pod pritiskom,<br />sadrže termički nepromenjene aktivne komponente, te se<br />poslednjih godina sve vi&scaron;e primenjuju u farmaceutskoj i<br />prehrambenoj industriji.<br />Cilj ove doktorske disertacije je da se ispita mogućnost<br />inkorporiranja ekstrakta nevena (<em>Calendula officinalis</em> L.), kao<br />farmakolo&scaron;ki aktivne materije, u mikrokapsule sa ciljem za&scaron;tite<br />od spolja&scaron;njih uticaja, produžetka njegovog delovanja i<br />pro&scaron;irenja mogućnosti primene.<br />Za dobijanje ekstrakata nevena primenjeni su postupci<br />ekstrakcije ugljendioksidom u tečnom i superkritičnom stanju.<br />Definisani su uslovi pri kojima je moguće dobiti ekstrakat sa<br />visokim sadržajem etarskog ulja, nosiocem gastro-intestinalnog<br />delovanja (200 bar, 40^oC). Totalni ekstrakt dobijen pod ovim<br />uslovima ekstrakcije je odabran za dobijanje mikrokapsula.<br />Ispitivana je mogućnosti primene polimer&ndash;PAM interakcije<br />nejonskih derivata celuloze- hidroksipropilmetil celuloze<br />(HPMC) i anjonske PAM- natrijum dodecilsulfata (SDS), za<br />formiranje omotača mikrokapsula. Primenom konduktometrijske<br />i viskozimetrijske metode, određene su karakteristične<br />koncentracije pri kojima HPMC&ndash;SDS interakcija započinje i<br />zavr&scaron;ava se. Definisan je uticaj osobina molekula HPMC<br />(molekulska masa, stepen supstitucije, vrsta supstituenta) i<br />temperature na &scaron;irinu intervala interakcije i obja&scaron;njeni<br />mehanizmi njihovog povezivanja, sa osvrtom na strukturu i<br />osobine formiranih HPMC/SDS komleksa. Reolo&scaron;kim<br />ispitivanjima pri različitim uslovima definisane su promene u<br />pona&scaron;anju sistema u zavisnosti od HPMC&ndash;SDS interakcije.<br />Ispitivan je uticaj interakcije na osobine 20% emulzija<br />suncokretovog ulja u vodi određivanjem njihovih reolo&scaron;kih<br />osobina, veličina i raspodela veličina kapi i praćenjem<br />stabilnosti. Utvrđeno je da se u oblasti najizraženije HPMC&ndash;SDS interakcije, odnosno kada se na granici faza ulje-voda<br />nalazi umrežen HPMC/SDS kompleks, dobijaju emulzije<br />najveće stabilnosti, sa njajmanjim srednjim prečnikom kapi.<br />Su&scaron;enjem emulzija, primenom spray drying postupka,<br />dobijene su mikrokapsule uljnog sadržaja, stabilizovane<br />kompleksom HPMC/SDS. Najbolje karakteristike mikrokapsula<br />(mehanička otpornost, morfolo&scaron;ke karakteristike, sposobnost<br />redispergovanja, veličina i raspodela veličina čestica i količina<br />inkapsuliranog ulja), dobijene u oblasti najizraženije interakcije.<br />Dodatak odabranog CO₂ ekstrakta nevena u uljnu fazu<br />emulzija ne menja značajno njihove osobine, kao ni osobine iz<br />njih dobijenih mikrokapsula.<br />Ispitivanja sprovedena u ovoj doktorskoj disertaciji<br />pokazala su da se osobine kompleksa polimer/PAM mogu<br />iskoristiti za mikrokapsulaciju ulja kao nosača farmakolo&scaron;ki<br />aktivnih materija.</p> / <p>Contemporary global trends in food- functional food,<br />pharmaceutical and cosmetic industry as well have been<br />focused on a wider medical plants extracts application during<br />the recent decade. Plant extracts obtained by means of carbon<br />dioxide under high pressure contained all unchanged active<br />compounds from plant, so that they have became more<br />popular for application in food and pharmaceuticals recently.<br />The aim of this thesis was to investigate the possibility to<br />incorporate marigold extract (<em>Calendula officinalis</em> L.), as a<br />pharmacologicaly active compound, into microcapsules in<br />order to protect them from surrounding medium, improve<br />their activity and enlarge application.<br />Marigold extracts were obtained by means of carbon<br />dioxide- CO2 under subcritical and supercritical conditions.<br />Extraction conditions under which obtained extract has high<br />content of essential oil, responsible for gastrointestinal<br />activity, were determined (200bar and 40^oC). Total extract<br />obtained under such conditions, was chosen for microcapsule<br />preparation. Application possibility of polymer&ndash;surfactant<br />interaction between non-ionic cellulose derivativehydroxypropylmethyl<br />cellulose (HPMC) and anionic<br />surfactant- sodium dodecylsulfate (SDS) to microcapsule<br />wall formation was investigated. Characteristic<br />concentrations at which interaction starts and ends were<br />determined by means of conductometric and viscometric<br />measurements. The influence of HPMC molecular<br />characteristics (molecular weight, degree of substitution and<br />substituents kind) and temperature on interaction were<br />determined and, considering the structure and characteristics<br />of HPMC/SDS complexes, binding mechanism was<br />explained. The changes in HPMC-SDS system caused by<br />their interaction were defined by rheological investigations<br />that took place under various conditions.<br />The influence of interaction on the properties of 20%<br />sunflower oil/water emulsion was investigated by rheology<br />measurement, particle size and particle size distribution<br />determination and stability testing. It was provided that<br />emulsions prepared in the region of pronounced HPMC&ndash;SDS<br />interaction, where HPMC/SDS complex is adsorbed at the</p><p>o/w interface, have highest stability and smallest particle<br />mean diameter.<br />Microcapsules were obtained by spray drying of<br />emulsions stabilized with HPMC/SDS complex. The best<br />characteristics (mechanical resistance, morphological<br />characteristics, redispersing ability, particle size and particle<br />size distribution and amount of encapsulated oil) have<br />microcapsules obtained in the region of most pronounced<br />interaction.<br />Addition of marigold CO₂ extract in to the oil phase of<br />emulsions has no significant influence neither on their, nor on<br />corresponding microcapsules characteristics<br />Investigations conducted in this thesis showed that<br />characteristics of polymer/surfactant complexes can be used<br />in microencapsulation of oil as carrier of pharmacologically<br />active compounds</p>

The expected outcome of this project is to develop a general strategy to functionalize dispersions, by noncovalent adsorption of HMW surfactants, ultimately for applications such as hydrophobic coatings with high hiding power and hardness, improved mechanical properties via pigment-latex interactions, improved substrate adhesion or improved freeze-thaw stability. So far, we have produced poly (methyl methacrylate-co-butyl acrylate) latexes in the presence of HMW surfactants via emulsion polymerization and demonstrated stronger adsorption of HMW surfactants on particle surface than sodium dodecyl sulfate (SDS). In addition, we have developed surfactant-free latexes, poly (methyl methacrylate-co-butyl acrylate-co-methacrylic acid), as models for post functionalization with high molecular weight surfactants. The successful transfer of surfactants onto particle surface from liquid crystals was indicated by the increase in zeta potential and confirmed via chemical shifts variation in 1H NMR spectra. Additionally, the HMW surfactants were used for dispersing hydrophobic inorganic particles, such as hydrophobic carbon black, in aqueous phase, providing an indication of the general applicability and versatility of our approach.

No description available.

Content: Surfactants are used as auxiliaries in every wet processing process of leather production and discharged into wastewater, which would cause potential ecological risks. In this paper, fresh luminescent bacillus liquids were employed to evaluate the ecological toxicity of six surfactants, including anionic, cationic and non-ionic surfactants, and mixture of two typical ionic and nonionic surfactants after a 15-min exposure period. Non-ionic surfactants AEO and Tween80 showed slight light inhibition ie.10-35% to luminescent bacteria. The toxicity of anionic surfactants with polar sulfonic group was: penetrant T(EC50=406.81mg/L) ＞SDBS(EC50=573.37mg/L). The toxicity of cationic surfactants was: DTAB（EC50=10.68mg/L）＞SKC （EC50=73.96mg/L）. The addition of nonionic surfactants reduced the toxicity of ionic surfactants. 1-1 mixture of SKC and AEO: EC50=80.17mg/L, 1-1 mixture of SDBS and AEO: EC50=624.34mg/L. These results provided ecological parameters for the selection of surfactants in the process of ecological leather production. Take-Away: 1. The toxicity measurement by luminescent bacteria, which is simple and convenient, was used to evaluate the toxicity of surfactants, and the reproducibility was improved in our study. 2. The toxicities of six different surfactants was evaluated by EC50 which provided ecological parameters for the selection of surfactants in the process of ecological leather production.

Content: Surfactants of different ionic nature are used in virtually all steps of leather production. In processes like soaking, degreasing and wool washing, tremendous amounts of surfactants are applied and to a great extent discharged into the tannery effluent. In order to improve the sustainability of leather processing, there is a constant search for more efficient, environmentally friendly emulsifiers, which give superior results already in smaller usage amounts. By introduction of propylene oxide based lipophilic linkers between the hydrophilic head and hydrophobic tail, the wetting and emulsion capability of a surfactant can be increased significantly. The resulting surfactants, so called extended surfactants, are generally more hydrophobic and have an extended tail, which reaches further into the oil face without scarifying the water solubility, what would be the results when increasing the alkyl chain. Thus, the use of lipophilic linker changes the emulsion on a structural level. Extended surfactants have been found to be superior in various applications, including textile laundry or tertiary oil recovery. In the present work, the efficiency of various types of non-ionic and anionic extended surfactants is demonstrated in various stages of leather making. Model surfactants with lipophilic linkers are compared to their analogues without linker molecules. In many processes, significantly improved surfactant efficiencies are found making this group of molecules an interesting topic for further exploitation. Take-Away: Significantly improved surfactant efficiency for more sustainable leather processing