The fields of biodiesel and bioethanol research and development have largely developed independently of one another. Opportunities exist for greater integration of these processes that may result in decreased costs of production for both fuels.To that end, this work addresses the use of the starches and glycerol from processed algal biomass as substrates for fermentation by the yeasts <ital>Saccharomyces cerevisiae</ital> and <ital>Pachysolen tannophilus,</ital> respectively. Ethanol producers commonly employ the former yeast for ethanol production and include the latter yeast among candidate species for cellulosic ethanol production.A simple 95% ethanol extraction at 70°C followed by sulfuric acid hydrolysis at 121°C and 2 atm proved a sufficient pretreatment for <ital>S. cerevisiae</ital> fermentation of starch from <ital>Chlamydomonas reinhardtii</ital> mutant <ital>cw15.</ital> The maximum rate of ethanol production was observed as 14 mL/g-h and a maximum concentration of 0.9±0.01% (m/v) was observed by 28 hours. Some starch appeared invulnerable to hydrolysis.<ital>P. tannophilus</ital> fermentation of glycerol, both independently and among mixed substrates, was likewise demonstrated. It was found that glucose consumption preceded that of glycerol and xylose, but that the latter two substrates were consumed concurrently. Under aerobic, batch conditions, the maximum specific growth rate of the species on a 2% glycerol substrate was observed as 0.04/hr and the yield coefficient for conversion of glycerol to ethanol was 0.07 g/g. While the maximum observed concentration of ethanol in the glycerol-only fermentation was 0.1% m/v, that in mixed media containing 2% each glucose, xylose, and glycerol was 1.5%.Also investigated here was the flocculation of a mutant species of the algae <ital>C. reinhardtii</ital> by a combination of methanol and calcium. Algae harvest is typically an energy-intensive process, but the technique demonstrated here is not. Complete flocculation of cells was observed with only 5 minutes of mixing and less than 10 minutes of settling using 12 mM CaCl₂ and 4.6% methanol. Ethanol was observed to operate in the same capacity, intimating another area in which yeast bioethanol and algal biodiesel processes might enable one another. During growth, either an inhibitor of flocculation was produced or a facilitator was consumed.

Several bacteria were isolated from the bottom sediments of Tyume River and investigated for bioflocculant production potentials. Kaolin clay suspension (4 g/l) was used to measure the flocculating activity and three of the positive isolates were identified by 16S rRNA gene nucleotide sequence analyses and the sequences deposited in GenBank as Streptomyces sp Gansen (accession number HQ537129), Brachybacterium sp UFH (accession number HQ537131.), and Cellulomonas sp Bola (accession number HQ537132). Streptomyces sp Gansen exhibited its maximum flocculating activity using lactose (85% activity), peptone (76.3% activity), Ca2+ as sole sources of carbon, nitrogen and cations respectively, and at a neutral pH of 7.0, while, the bioflocculant produced by Brachybacterium sp UFH with glucose, urea and Ca2+ as carbon, nitrogen and cations sources yielded 82% and 97% flocculation activity respectively at a neutral pH. Also, glucose (73.2% activity), ammonium chloride (78.2% activity) and Ca2+ resulted in optimal production of bioflocculant by Cellulomonas sp Bola, also at a neutral pH. Chemical analysis confirmed that bioflocculant produced by Streptomyces Gansen is a polysaccharide while Brachybacterium sp UFH and Cellulomonas sp Bola produces a glycoprotein compound. This freshwater actinomycetes appears to have a tremendous potential as sou rces of new bioflocculants.

Typescript (photocopy). / Digitized by Kansas Correctional Industries

Este trabalho apresenta uma extensa revisão bibliográfica enfocando os aspectos químicos e cinéticos da coagulação e floculação de águas contendo cor e turbidez. São Fornecidos dados de um grande número de ensaios de floculação realizados em instalação especialmente construída para estudar a coagulação e floculação de diversos tipos de águas preparadas em laboratório e naturais, contendo turbidez e cor. Como resultado, é proposta uma metodologia para a determinação de calores ótimos de dosagem de coagulante e respectivo pH, úteis para o tratamento de águas de abastecimento através da coagulação nos mecanismos de adsorção-neutralização e varredura, seguidos de floculação e sedimentação. Ainda com base no trabalho experimental realizado, é proposto um novo modelo matemático para correlacionar os dados do gradiente de velocidade ótimo com os períodos de floculação. Este modelo constitui-se em um aperfeiçoamento daquele apresentado anteriormente por ANDREU-VILLEGAS & LETTERMAN (4), acrescentando-se um novo parâmetro denominado gradiente de velocidade mínimo (G\'), para o qual obtêm-se crescentes eficiências de remoção de partículas floculentas por sedimentação com o aumento do período de floculação. / An extensive review of the literature, concerning chemical and kinetic aspects of coagulation and flocculation of several inicial qualitys of colored or turbid water is presented herein. An experimental work was carried out using a special facility to study all the aspects related to coagulation and flocculation of several types of shynthetic and natural waters. Based of the results obtained in this work, a new methodology to investigate optimum coagulant dosis and respective pH considering both coagulation mechanisms, adsorption-neutralization and sweep coagulation, is presented. In addition, a new methametical expression was derived to related optimum velocity gradient and mixing time for flocculation. This model is a refinement of that presented earlier by ANDREU-VILLEGAS & LETTERMAN (4), including a new parameter named minimum velocity gradient (G\') that permit an increase performance of the remotion of the inicial turbidity and color of water with the increase of the flocculation time.

For the majority of tailings substrates, flocculant adsorption proceeds through hydrogen bonding of the amide functionalities with neutral surfaces. However, flocculation of Bayer process residue solids takes place in highly caustic liquors, typically using high molecular weight polyacrylates. This represents an almost unique situation, and implies a totally different adsorption mechanism. Direct examination of polyacrylate adsorption within the complex matrix of real liquors and a mixture of residue phases is difficult, making it necessary to focus on a model substrate (hematite) and synthetic liquors (pH 13 at high ionic strength). Previous spectral studies have used ex situ techniques, with sample drying potentially altering the adsorbed species, leading to inconclusive results. This study presents for the first time direct in situ evidence of polyacrylate adsorption onto hematite obtained by Fourier Transform Infrared-Attenuated Total Reflection (FTIR-ATR) Spectroscopy. Adsorption and hence concentration of dilute polyacrylate solutions onto hematite-coated zinc selenide optics has provided spectra of adsorbed polymer under a range of conditions, unbiased by any contribution from the bulk polymer solution. Analysis of the polyacrylate carbon-oxygen stretching frequencies established differing modes of adsorption at low and high pH conditions. At pH 2 adsorption proceeded through bidentate chelation of the carboxylate to a surface ferric ion, facilitated through deprotonation of a carboxylic acid group and removal of a hematite surface hydroxyl group, i.e. chemisorption. Unshifted carboxyl peaks in the spectrum enabled the unadsorbed 'loops' and 'tails' to be distinguished from the adsorbed polymer, and represented at least 70% of the total polymer chain length. / In contrast, at pH 13 adsorption of polyacrylate occurs via physisorption and was only possible with the addition of electrolyte. This adsorption was enhanced with increasing electrolyte concentrations up to 1 M NaCl. The hematite surface charge was negative at high pH, however with increasing ionic strength the specific adsorption of Na+ ions decreased the negative surface charge, and at very high salt concentrations the surface became positively charged. For electrolyte with different monovalent cations, polymer adsorption increased in the order Li+ > Na+ > Cs+. The identity of the monovalent cation had no effect on the polymer solution dimensions but the ability to reduce the magnitude of the hematite surface charge followed the same trend. This finding is consistent with the 'structure making - structure breaking' model proposed by Berube and de Bruyn. At both high and low pH, polyacrylate exhibited adsorption isotherms that are best described by the Langmuir expression. Surface coverage was greatest at low pH due to more available surface sites and the adsorbed polymer conformation (a greater fraction of loops and tails). Adsorbed conformation and hence maximum adsorption was independent of molecular weight at low pH, however at high pH maximum adsorption increased with increased molecular weight, indicating an adsorbed polymer configuration exhibiting a greater degree of loops and tails. While the individual carboxylate-surface interaction was stronger at low pH than high pH, both were relatively weak. Despite this, none of the polymers could be removed by washing, demonstrating the strength and irreversibility of the multi-attached polymer molecules. / The stronger individual carboxylate-surface interactions at low pH is indicative of a higher activation energy of formation, and may be a contributing factor to the slower rate of adsorption at low pH. The rate of polyacrylate adsorption was dominated by mass transport limitations in all cases. The initial rate of adsorption was greater at lower polymer molecular weight, consistent with the relative polymer diffusion coefficients. This rate of adsorption was much less dependent on polymer molecular weight at high pH than at low pH, suggesting significantly different polymer-solvent interactions. It was clearly demonstrated that the sodium ion concentration within the high ionic strength Bayer liquors is more than sufficient to facilitate polyacrylate adsorption on bauxite residue. There is no need to postulate calcium bridging between the polymer and surface, as has been suggested in previous studies. Improved settling and clarity associated with the presence of calcium on residue surfaces is more likely due to enhanced particle coagulation prior to flocculation. FTIR-ATR has been shown to be an excellent tool for the in situ examination of polyacrylate adsorption onto hematite, and will be a powerful technique for the characterisation and subsequent comparison of the adsorption behaviour of other systems.

Commercial Magnafloc 1011and in-house synthesized Al-PAM were used as flocculants for model tailings, laboratory extraction tailings and tailings from paraffin froth treatment unit. The polymers were tested for their flocculation ability in settling and filtration. For model tailings, both polymers showed excellent ability to improve the settling and filtration performance. Magnafloc 1011 is found sensitive to overdosing, but Al-PAM is not sensitive to the dosage within the tested range. For the laboratory extraction tailings, both polymers showed excellent ability to enhance settling. Al-PAM performed very well as a filtration aid. The moisture of the cake obtained from tailings derived from a low fines ore was 6.6 1.2wt% and that from a high fines ore was 16.9 0.8wt%. However, Magnafloc 1011 was found not effective as a filtration aid. For the froth treatment tailings, Al-PAM improved the settling and filterability dramatically. Although the moisture of the cake obtained was 42.5wt%, no free water is seen visually in the cake. The solid cake is self-supportive and remains intact. This class of Al-PAM polymers can provide an alternative approach for oil sands tailings disposal that can potentially eliminate tailings ponds. / Chemical Engineering

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Modeling the transport and fate of spilled crude oil is important for estimating short and long-term toxicity effects in coastal ecosystems. This research project investigates the partitioning of hydrocarbons from a surface crude oil slick, the resurfacing of chemically dispersed crude oil droplets, the suitability of in-situ field instruments for oil and sediment characterization, and the aggregation and settling of dispersed oil and suspended sediments. An initial laboratory study was conducted to investigate apparent hydrocarbon solubility in petroleum/water systems. Mixing shear and initial crude oil layer thickness were related empirically to oil entrainment rate. A model describing hydrocarbons partitioned in colloidal and soluble phases was consistent with experimental data. A second laboratory study was conducted to investigate the influence of coalescence kinetics on mean droplet size and resurfacing rate of chemically dispersed crude oil droplets. Increased mean shear rates resulted in mean droplet diameters and oil resurfacing rates. A third laboratory study was conducted to compare particle size and fractal dimension measurements obtained using a submersible flow cytometer, an electrozone particle counter, and a light scattering particle sizer. Measured particles included latex beads, crude oil, clay, crude oil-clay aggregates, and crude oil-silica aggregates. Tested instruments gave consistent size measurements for all particle systems, suggesting their suitability for sizing marine particles. To describe the aggregation kinetics of oil-sediment systems, a modified Smoluchowski model based on coalesced sphere (CS) assumptions was developed. Observed collision efficiency values (αOBS) were related to collision efficiency values for single particle type systems (αHOMO) and those for two particle type systems (αHET) using a probabilistic approach. For clay and crude oil, αHOMO values were higher than the αHOMO value for silica. Clay-oil and silica-oil have similar αHET values. Thus, crude oil can significantly increase the aggregation rates of noncohesive sediments such as silica. The CS model above was modified to incorporate sediment fractal geometry. The ability of this modified coalesced fractal sphere (mCFS) model to fit experimental data sets was better than that of a coalesced sphere (CS) model. Because of their reduced settling rates, sediments with lower fractal dimension form more aggregate with dispersed oil.

Concentric rotating cylinder and turbulent mixing devices have been frequently used in studying mixing and particle coagulation. However, these apparatus develop simple laminar flow (concentric rotating cylinders) or do not have well-defined flow (turbulent mixing devices). In this work, the eccentric rotating cylinder apparatus was investigated to find applicability for the improved study of coagulation based on the modified analytical solution of Ballal and Rivlin. Various eccentricity ratios, rotation speeds and viscosities were simulated to obtain optimum operating conditions. Inertial forces working on the fluid increased as the eccentricity ratio and rotation speed increase. As inertial forces increase, the eddy developed in wide clearance was more skewed in the direction of rotation. Both root-mean-square velocity gradient and average principal strain-rate, were increased by increasing eccentricity ratio. avaerage principal strain-rate were linearly increased as rotation speed increases, which suggested that average prinipal strain-rate can properly represent mixing intensity. Comparison of average principal strain-rate and RMS velocity gradient revealed that RMS velocity gradient overestimated mixing intensity and its error increased as eccentricity ratio increases. This study showed that the eccentric rotating cylinder apparatus has a non-uniform velocity distribution with well-defined fluid dynamics. Therefore, the eccentric rotating cylinder apparatus can be applicable as a model flocculator. However, in order to achieve reliable model predictability, the fluid Reynolds number must be below 200.