Characterisation of red mud and seawater neutralised red mud using vibrational spectroscopic techniques

Bauxite refinery residues are derived from the Bayer process by the digestion of crushed bauxite in concentrated caustic at elevated temperatures. Chemically, it comprises, in varying amounts (depending upon the composition of the starting bauxite), oxides of iron and titanium, residual alumina, sodalite, silica, and minor quantities of other metal oxides. Bauxite residues are being neutralised by seawater in recent years to reduce the alkalinity in bauxite residue, through the precipitation of hydrotalcite-like compounds and some other Mg, Ca, and Al hydroxide and carbonate minerals. A combination of X-ray diffraction (XRD) and vibrational spectroscopy techniques, including mid-infrared (IR), Raman, near-infrared (NIR), and UV-Visible, have been used to characterise bauxite residue and seawater neutralised bauxite residue. Both the ferrous (Fe2+) and ferric (Fe3+) ions within bauxite residue can be identified by their characteristic NIR bands, where ferrous ions produce a strong absorption band at around 9000 cm-1, while ferric ions produce two strong bands at 25000 and 14300 cm-1. The presence of adsorbed carbonate and hydroxide anions can be identified at around 5200 and 7000 cm-1, respectively, attributed to the 2nd overtone of the 1st fundamental overtones observed in the mid-IR spectra. The complex bands in the Raman and mid-IR spectra around 3500 cm-1 are assigned to the OH stretching vibrations of the various oxides present in bauxite residue, and water. The combination of carbonate and hydroxyl units and their fundamental overtones give rise to many of the features of the NIR spectra.

Settling behaviours of low alumina/caustic ratios during seawater neutralisation of Bayer liquor

Factors that affect the settleability of seawater neutralised bauxite refinery residues are poorly understood, in particular, the settleability of precipitates in the absence of red mud and those formed with different alumina/caustic (AC) ratios. The influence of temperature, AC ratio, caustic concentration and the volumetric ratio of seawater on the settleability of seawater neutralisation precipitates and their respective compositions and stabilities have been determined. An array of techniques have been used to determine the composition and stability of precipitates and include pH, conductivity, inductively coupled plasma optical emission spectroscopy, infrared spectroscopy and X-ray diffraction. Temperature has been shown to have a significant influence on the settleability and calcium carbonate phase distributions in precipitates, as well as the overall stability of the precipitates. More complex phase compositions have also been found for Bayer liquors with lower AC ratios. The caustic concentration and temperature of the reaction have the greatest influence on the settling efficiency of the precipitates. Assessments on the chemical stability of the precipitates, precipitate settleability and discharge water quality have been made. In addition, productivity and environmental impacts caused by changes in precipitate settleability have also been considered.

Solution chemistry impacts on the seawater neutralisation process: Benefits of nanofiltered seawater and reverse osmosis brine

It is well known that the neutralisation of Bayer liquor with seawater causes the precipitation of stable alkaline products and a reduction in pH and dissolved metal concentrations in the effluent. However, there is limited information available on solution chemistry effects on the stability and reaction kinetics of these precipitates. This investigation shows the influence of reactive species (magnesium and calcium) in seawater on precipitate stabilities and volumetric efficiencies during the neutralisation of bauxite refinery residues. Correlations between synthetic seawater solutions and real samples of seawater (filtered seawater, nanofiltered seawater and reverse osmosis brine) have been made. These investigations have been used to confirm that alternative seawater sources can be used to increase the productivity potential of the neutralisation process with minimal implications on the composition and stability of precipitates formed. The volume efficiency of the neutralisation process using synthetic analogues has been shown to be almost directly proportional with the concentration of magnesium. This was further confirmed in the nanofiltered seawater and reverse osmosis brine that showed increases in the efficiency of neutralisation by factors of 3 and 2 compared to seawater, which corresponds with relatively the same increase in the concentration of magnesium in these alternative seawater sources. An assessment of the chemical stability of the precipitates, volumetric efficiency, and discharge water quality have been determined using numerous techniques that include pH, conductivity, inductively coupled plasma optical emission spectroscopy, infrared spectroscopy, thermogravimetric analysis coupled to mass spectrometry and X-ray diffraction. Correlations between synthetic solution compositions and alternative seawater sources have been used to determine if alternative seawater sources are potential substitutes for seawater based on improvements in productivity, implementation costs, savings to operations and environmental benefits.

Microbial activities in boreal soils: Biodegradation of organic contaminants at low temperature and ammonia oxidation

This thesis deals with the response of biodegradation of selected anthropogenic organic contaminants and natural autochthonous organic matter to low temperature in boreal surface soils. Furthermore, the thesis describes activity, diversity and population size of autotrophic ammonia-oxidizing bacteria (AOB) in a boreal soil used for landfarming of oil-refinery wastes, and presents a new approach, in which the particular AOB were enriched and cultivated in situ from the landfarming soil onto cation exchange membranes. This thesis demonstrates that rhizosphere fraction of natural forest humus soil and agricultural clay loam soil from Helsinki Metropolitan area were capable of degrading of low to moderate concentrations (0.2 50 µg cm-3) of PCP, phenanthrene and 2,4,5-TCP at temperatures realistic to boreal climate (-2.5 to +15 °C). At the low temperatures, the biodegradation of PCP, phenanthrene and 2,4,5-TCP was more effective (Q10-values from 1.6 to 7.6) in the rhizosphere fraction of the forest soil than in the agricultural soil. Q10-values of endogenous soil respiration (carbon dioxide evolution) and selected hydrolytic enzyme activities (acetate-esterase, butyrate-esterase and β-glucosidase) in acid coniferous forest soil were 1.6 to 2.8 at temperatures from -3 to +30 °C. The results indicated that the temperature dependence of decomposition of natural autochthonous soil organic matter in the studied coniferous forest was only moderate. The numbers of AOB in the landfarming (sandy clay loam) soil were determined with quantitative polymerase chain reaction (real-time PCR) and with Most Probable Number (MPN) methods, and potential ammonium oxidation activity was measured with the chlorate inhibition technique. The results indicated presence of large and active AOB populations in the heavily oil-contaminated and urea-fertilised landfarming soil. Assessment of the populations of AOB with denaturing gradient gel electrophoresis (DGGE) profiling and sequence analysis of PCR-amplified 16S rRNA genes showed that Nitrosospira-like AOB in clusters 2 and 3 were predominant in the oily landfarming soil. This observation was supported by fluorescence in situ hybridization (FISH) analysis of the AOB grown on the soil-incubated cation-exchange membranes. The results of this thesis expand the suggested importance of Nitrosospira-like AOB in terrestrial environments to include chronically oil-contaminated soils.

Ecological risk assessment of pollution in sediment on benthic fauna in coast of Bandar Abbas

Ecological risk assessment is determination of the probability of an adverse effect occurring to an ecological system. This investigation was carried out to assess the ecological risk of sediment in coast of Bandar Abbass in 9 stations including Shilat Jetty, Hotel Amin, Poshte-Shahr, Souro, Bahonar Jetty, Powerhouse, Refinery and Rajaee Jetty from autumn 2013 to summer 2014. Results showed that Polychaete with 1177 , 1109 , 414 , 573 , ind.m2 in autumn 91 , winter 91 , spring 92 and summer 92 were the most abundant in frequency respectively. Among ecological indices, the Margalof that ranged from 4 to 7 was in a good situation while Shanoon and Berger – Parker with 1.2 (at most) and 0.32 (at least) respectively indicated an environment with probable stress. Heavy metal distribution obtained as Cd>Pb>Cu>Zn in sediment. In tissue, the distribution of heavy metals were as Crab>polychaete>Bivalve>gastropod for Pb, Gastropod>Bivalve>Polychaete>Crab for Cd, Gastropod>Crab>Polychaete>Bivalve for Cu and Gastropod>Bivalve>Crab>Polychaete for Zn. Maximum and Minimum of TOM obtained 10.16 and 1.96 percent in Posht-e-Shahr and shilat Jetty respectively and clay was the dominant grain in most area. Bioaccumulation coefficient of Zn and Cu was high in all stations. Igeo as a single index was high for Cd indicating a high risk in all stations. Potential Ecological Risk was high for Cu and Zn and goes increasingly from shilat Jetty to Rajee Jetty but goes down for Pb. Pollution index for Cu and Pb was nearly the same as Potential Ecological Risk but for Zn goes constantly. Among PAH, 5-ring and 6-ring PAhs were more concentrate comparison to other compounds in sediment. 2-ring and 3-ring, 3-ring, 4-ring and 5-ring and 5-ring PAHs were more concentrate in Gastropod, Bivalve, Crab and Polychaete respectively. HI as an index of PAH obtained 1. Ecological Risk Indices showed that the heavy metals are a serious risk for invertebrate in sediment but PAHs are not a risk for benthic community.

Implications of local lifecycle analyses and low carbon fuel standard design on gasohol transportation fuels

State and regional policies, such as low carbon fuel standards (LCFSs), increasingly mandate that transportation fuels be examined according to their greenhouse gas (GHG) emissions. We investigate whether such policies benefit from determining fuel carbon intensities (FCIs) locally to account for variations in fuel production and to stimulate improvements in FCI. In this study, we examine the FCI of transportation fuels on a lifecycle basis within a specific state, Minnesota, and compare the results to FCIs using national averages. Using data compiled from 18 refineries over an 11-year period, we find that ethanol production is highly variable, resulting in a 42% difference between carbon intensities. Historical data suggests that lower FCIs are possible through incremental improvements in refining efficiency and the use of biomass for processing heat. Stochastic modeling of the corn ethanol FCI shows that gains in certainty due to knowledge of specific refinery inputs are overwhelmed by uncertainty in parameters external to the refiner, including impacts of fertilization and land use change. The LCA results are incorporated into multiple policy scenarios to demonstrate the effect of policy configurations on the use of alternative fuels. These results provide a contrast between volumetric mandates and LCFSs. © 2011 Elsevier Ltd.

Effects of ethanol on vehicle energy efficiency and implications on ethanol life-cycle greenhouse gas analysis.

Bioethanol is the world's largest-produced alternative to petroleum-derived transportation fuels due to its compatibility within existing spark-ignition engines and its relatively mature production technology. Despite its success, questions remain over the greenhouse gas (GHG) implications of fuel ethanol use with many studies showing significant impacts of differences in land use, feedstock, and refinery operation. While most efforts to quantify life-cycle GHG impacts have focused on the production stage, a few recent studies have acknowledged the effect of ethanol on engine performance and incorporated these effects into the fuel life cycle. These studies have broadly asserted that vehicle efficiency increases with ethanol use to justify reducing the GHG impact of ethanol. These results seem to conflict with the general notion that ethanol decreases the fuel efficiency (or increases the fuel consumption) of vehicles due to the lower volumetric energy content of ethanol when compared to gasoline. Here we argue that due to the increased emphasis on alternative fuels with drastically differing energy densities, vehicle efficiency should be evaluated based on energy rather than volume. When done so, we show that efficiency of existing vehicles can be affected by ethanol content, but these impacts can serve to have both positive and negative effects and are highly uncertain (ranging from -15% to +24%). As a result, uncertainties in the net GHG effect of ethanol, particularly when used in a low-level blend with gasoline, are considerably larger than previously estimated (standard deviations increase by >10% and >200% when used in high and low blends, respectively). Technical options exist to improve vehicle efficiency through smarter use of ethanol though changes to the vehicle fleets and fuel infrastructure would be required. Future biofuel policies should promote synergies between the vehicle and fuel industries in order to maximize the society-wise benefits or minimize the risks of adverse impacts of ethanol.

Development of a triple stage heat transformer for the recycling of low temperature heat energy

Absorption heat transformers are thermodynamic systems which are capable of recycling industrial waste heat energy by increasing its temperature. Triple stage heat transformers (TAHTs) can increase the temperature of this waste heat by up to approximately 145˚C. The principle factors influencing the thermodynamic performance of a TAHT and general points of operating optima were identified using a multivariate statistical analysis, prior to using heat exchange network modelling techniques to dissect the design of the TAHT and systematically reassemble it in order to minimise internal exergy destruction within the unit. This enabled first and second law efficiency improvements of up to 18.8% and 31.5% respectively to be achieved compared to conventional TAHT designs. The economic feasibility of such a thermodynamically optimised cycle was investigated by applying it to an oil refinery in Ireland, demonstrating that in general the capital cost of a TAHT makes it difficult to achieve acceptable rates of return. Decreasing the TAHT's capital cost may be achieved by redesigning its individual pieces of equipment and reducing their size. The potential benefits of using a bubble column absorber were therefore investigated in this thesis. An experimental bubble column was constructed and used to track the collapse of steam bubbles being absorbed into a hotter lithium bromide salt solution. Extremely high mass transfer coefficients of approximately 0.0012m/s were observed, showing significant improvements over previously investigated absorbers. Two separate models were developed, namely a combined heat and mass transfer model describing the rate of collapse of the bubbles, and a stochastic model describing the hydrodynamic motion of the collapsing vapour bubbles taking into consideration random fluctuations observed in the experimental data. Both models showed good agreement with the collected data, and demonstrated that the difference between the solution's temperature and its boiling temperature is the primary factor influencing the absorber's performance.

Effect of Bauxol on properties of cement pastes

This paper presents the results of an experimental investigation carried out to evaluate the influence of Bauxsol, an artificially neutralised bauxite refinery residue (NBRR), on various properties of cement pastes. It was found that the NBRR does not have any pozzolanic properties and hence cannot be used as a supplementary cementitious material in concrete. In order to evaluate the effect of adding the product to Portland cement (PC) pastes, fresh properties (i.e. standard consistency and slump), setting time and heat of hydration were measured. In addition, its influence on chemical changes and compressive strength was investigated. It was found that the addition of this NBRR resulted in a decrease in compressive strength beyond 7 days. The setting time decreased with an increase in NBRR content in PC pastes. The rate of heat evolution for NBRR pastes was greater than that of the PC pastes, but a corresponding increase in the quantity of calcium hydroxide was not found. Therefore, it was concluded that unidentified hydration products when Bauxsol was used in PC pastes might have been the reason for the decrease in setting times.

Combination of CFD and DOE to analyse solid particle erosion in elbows

Solid particle erosion is a major concern in the engineering industry, particularly where transport of slurry flow is involved. Such flow regimes are characteristic of those in alumina refinement plants. The entrainment of particulate matter, for example sand, in the Bayer liquor can cause severe erosion in pipe fittings, especially in those which redirect the flow. The considerable costs involved in the maintenance and replacement of these eroded components led to an interest in research into erosion prediction by numerical methods at Rusal Aughinish alumina refinery, Limerick, Ireland, and the University of Limerick. The first stage of this study focused on the use of computational fluid dynamics (CFD) to simulate solid particle erosion in elbows. Subsequently an analysis of the factors that affect erosion of elbows was performed using design of experiments (DOE) techniques. Combining CFD with DOE harnesses the computational power of CFD in the most efficient manner for prediction of elbow erosion. An analysis of the factors that affect the erosion of elbows was undertaken with the intention of producing an erosion prediction model. © 2009 Taylor & Francis.

Performance assessment of cascade control loopswith non-Gaussian disturbances using entropy information

Cascade control is one of the routinely used control strategies in industrial processes because it can dramatically improve the performance of single-loop control, reducing both the maximum deviation and the integral error of the disturbance response. Currently, many control performance assessment methods of cascade control loops are developed based on the assumption that all the disturbances are subject to Gaussian distribution. However, in the practical condition, several disturbance sources occur in the manipulated variable or the upstream exhibits nonlinear behaviors. In this paper, a general and effective index of the performance assessment of the cascade control system subjected to the unknown disturbance distribution is proposed. Like the minimum variance control (MVC) design, the output variances of the primary and the secondary loops are decomposed into a cascade-invariant and a cascade-dependent term, but the estimated ARMA model for the cascade control loop based on the minimum entropy, instead of the minimum mean squares error, is developed for non-Gaussian disturbances. Unlike the MVC index, an innovative control performance index is given based on the information theory and the minimum entropy criterion. The index is informative and in agreement with the expected control knowledge. To elucidate wide applicability and effectiveness of the minimum entropy cascade control index, a simulation problem and a cascade control case of an oil refinery are applied. The comparison with MVC based cascade control is also included.

NMR in the characterization of heavy residual procedural streams

The main objective of this work was to monitor a set of physical-chemical properties of heavy oil procedural streams through nuclear magnetic resonance spectroscopy, in order to propose an analysis procedure and online data processing for process control. Different statistical methods which allow to relate the results obtained by nuclear magnetic resonance spectroscopy with the results obtained by the conventional standard methods during the characterization of the different streams, have been implemented in order to develop models for predicting these same properties. The real-time knowledge of these physical-chemical properties of petroleum fractions is very important for enhancing refinery operations, ensuring technically, economically and environmentally proper refinery operations. The first part of this work involved the determination of many physical-chemical properties, at Matosinhos refinery, by following some standard methods important to evaluate and characterize light vacuum gas oil, heavy vacuum gas oil and fuel oil fractions. Kinematic viscosity, density, sulfur content, flash point, carbon residue, P-value and atmospheric and vacuum distillations were the properties analysed. Besides the analysis by using the standard methods, the same samples were analysed by nuclear magnetic resonance spectroscopy. The second part of this work was related to the application of multivariate statistical methods, which correlate the physical-chemical properties with the quantitative information acquired by nuclear magnetic resonance spectroscopy. Several methods were applied, including principal component analysis, principal component regression, partial least squares and artificial neural networks. Principal component analysis was used to reduce the number of predictive variables and to transform them into new variables, the principal components. These principal components were used as inputs of the principal component regression and artificial neural networks models. For the partial least squares model, the original data was used as input. Taking into account the performance of the develop models, by analysing selected statistical performance indexes, it was possible to conclude that principal component regression lead to worse performances. When applying the partial least squares and artificial neural networks models better results were achieved. However, it was with the artificial neural networks model that better predictions were obtained for almost of the properties analysed. With reference to the results obtained, it was possible to conclude that nuclear magnetic resonance spectroscopy combined with multivariate statistical methods can be used to predict physical-chemical properties of petroleum fractions. It has been shown that this technique can be considered a potential alternative to the conventional standard methods having obtained very promising results.

Bioremediation of petroleum sludge through Phytoremediation.Land farming and Microbial enhanced oil separation

The objective of this research is to study the feasibility of bioremediating the oily sludge from a refinery site. Three different methods of waste treatment were tried i.e. phytoremediation, land farming and microbial enhanced oil separation in laboratory scale treatment systems. A multiprocess approach by combination of phytoremediation, biostimulation and microbial enhanced oil separation is also presented. The methods of analysis, experimental procedure, and results are incorporated into five chapters of this thesis entitled "Bioremediation of petroleum sludge through phytoremediation, land farming and microbial enhanced oil separation.

Structural characterization of supported nanocrystalline ZnO thin films prepared by dip-coating

Nanocrystalline ZnO thin films prepared by the sol-gel dip-coating technique were characterized by grazing incidence X-ray diffraction (GIXD), atomic force microscopy (AFM), X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS). The structures of several thin films subjected to (i) isochronous annealing at 350, 450 and 550 degrees C, and (ii) isothermal annealing at 450 degrees C during different time periods, were characterized. The studied thin films are composed of ZnO nanocrystals as revealed by analysing several GIXD patterns, from which their average sizes were determined. Thin film thickness and roughness were determined from quantitative analyses of AFM images and XR patterns. The analysis of XR patterns also yielded the average density of the studied films. Our GISAXS study indicates that the studied ZnO thin films contain nanopores with an ellipsoidal shape, and flattened along the direction normal to the substrate surface. The thin film annealed at the highest temperature, T = 550 degrees C, exhibits higher density and lower thickness and nanoporosity volume fraction, than those annealed at 350 and 450 degrees C. These results indicate that thermal annealing at the highest temperature (550 degrees C) induces a noticeable compaction effect on the structure of the studied thin films. (C) 2011 Elsevier B.V. All rights reserved.

Metastable Phase Diagram of Nanocrystalline ZrO(2)-Sc(2)O(3) Solid Solutions

We have investigated the crystal structures and phase transitions of nanocrystalline ZrO(2)-1 to -13 mol % Sc(2)O(3) by synchrotron X-ray powder diffraction and Raman spectroscopy. ZrO(2)-Sc(2)O(3) nanopowders were synthesized by using a stoichiometric nitrate-lysine get-combustion route. Calcination processes at 650 and at 850 degrees C yielded nanocrystalline materials with average crystallite sizes of (10 +/- 1) and (25 +/- 2) nm, respectively. Only metastable tetragonal forms and the cubic phase were identified, whereas the stable monoclinic and rhombohedral phases were not detected in the compositional range analyzed in this work. Differently from the results of investigations reported in the literature for ZrO(2)-Sc(2)O(3) materials with large crystallite sizes, this study demonstrates that, if the crystallite sizes are small enough (in the nanometric range), the metastable t ``-form of the tetragonal phase is retained. We have also determined the t`-t `` and t ``-cubic compositional boundaries at room temperature and analyzed these transitions at high temperature. Finally, using these results, we built up a metastable phase diagram for nanocrystalline compositionally homogeneous ZrO(2)-Sc(2)O(3) solid solutions that strongly differs from that previously determined from compositionally homogeneous ZrO(2)-Sc(2)O(3), Solid solutions with much larger crystallite sizes.