Treatment of oily wastewater by ultrafiltration: The effect of different operating and solution conditions

In many industries, such as petroleum production, and the petrochemical, metal, food and cosmetics industries, wastewaters containing an emulsion of oil in water are often produced. The emulsions consist of water (up to 90%), oils (mineral, animal, vegetable and synthetic), surfactants and other contaminates. In view of its toxic nature and its deleterious effects on the surrounding environment (soil, water) such wastewater needs to be treated before release into natural water ways. Membrane-based processes have successfully been applied in industrial applications and are considered as possible candidates for the treatment of oily wastewaters. Easy operation, lower cost, and in some cases, the ability to reduce contaminants below existing pollution limits are the main advantages of these systems. The main drawback of membranes is flux decline due tofouling and concentration polarisation. The complexity of oil-containing systems demands complementary studies on issues related to the mitigation of fouling and concentration polarisation in membranebased ultrafiltration. In this thesis the effect of different operating conditions (factors) on ultrafiltration of oily water is studied. Important factors are normally correlated and, therefore, their effect should be studied simultaneously. This work uses a novel approach to study different operating conditions, like pressure, flow velocity, and temperature, and solution properties, like oil concentration (cutting oil, diesel, kerosene), pH, and salt concentration (CaCl2 and NaCl)) in the ultrafiltration of oily water, simultaneously and in a systematic way using an experimental design approach. A hypothesis is developed to describe the interaction between the oil drops, salt and the membrane surface. The optimum conditions for ultrafiltration and the contribution of each factor in the ultrafiltration of oily water are evaluated. It is found that the effect on permeate flux of the various factors studied strongly depended on the type of oil, the type of membrane and the amount of salts. The thesis demonstrates that a system containing oil is very complex, and that fouling and flux decline can be observed even at very low pressures. This means that only the weak form of the critical flux exists for such systems. The cleaning of the fouled membranes and the influence of different parameters (flow velocity, temperature, time, pressure, and chemical concentration (SDS, NaOH)) were evaluated in this study. It was observed that fouling, and consequently cleaning, behaved differently for the studied membranes. Of the membranes studied, the membrane with the lowest propensity for fouling and the most easily cleaned was the regenerated cellulose membrane (C100H). In order to get more information about the interaction between the membrane and the components of the emulsion, a streaming potential study was performed on the membrane. The experiments were carried out at different pH and oil concentration. It was seen that oily water changed the surface charge of the membrane significantly. The surface charge and the streaming potential during different stages of filtration were measured and analysed being a new method for fouling of oil in this thesis. The surface charge varied in different stages of filtration. It was found that the surface charge of a cleaned membrane was not the same as initially; however, the permeability was equal to that of a virgin membrane. The effect of filtration mode was studied by performing the filtration in both cross-flow and deadend mode. The effect of salt on performance was considered in both studies. It was found that salt decreased the permeate flux even at low concentration. To test the effect of hydrophilicity change, the commercial membranes used in this thesis were modified by grafting (PNIPAAm) on their surfaces. A new technique (corona treatment) was used for this modification. The effect of modification on permeate flux and retention was evaluated. The modified membranes changed their pore size around 33oC resulting in different retention and permeability. The obtained results in this thesis can be applied to optimise the operation of a membrane plant under normal or shock conditions or to modify the process such that it becomes more efficient or effective.

Preparation of glasses and glass ceramics of heavy metal oxides containing silver: optical, structural and electrochemical properties

Silver containing heavy metal oxide glasses and glass ceramics of the system WO3-SbPO4-PbO-AgCl with different AgCl contents have been prepared and their thermal, structural and optical properties characterized. Glass ceramics containing metallic silver nanoparticles have been prepared by annealing glass samples at temperatures above the glass transition and analyzed by transmission electron microscopy and energy dispersive X-ray microanalysis. The presence of the metallic clusters has been also confirmed by the observation of a surface plasmon resonance band in the visible range. Cyclic voltammetric measurements indicated the presence of metallic silver into the glasses, even before to perform the thermal treatment.

METHANE DRY REFORMING OVER Ni SUPPORTED ON PINE SAWDUST ACTIVATED CARBON: EFFECTS OF SUPPORT SURFACE PROPERTIES AND METAL LOADING

The influence of metal loading and support surface functional groups (SFG) on methane dry reforming (MDR) over Ni catalysts supported on pine-sawdust derived activated carbon were studied. Using pine sawdust as the catalyst support precursor, the smallest variety and lowest concentration of SFG led to best Ni dispersion and highest catalytic activity, which increased with Ni loading up to 3 Ni atoms nm-2. At higher Ni loading, the formation of large metal aggregates was observed, consistent with a lower "apparen" surface area and a decrease in catalytic activity. The H2/CO ratio rose with increasing reaction temperature, indicating that increasingly important side reactions were taking place in addition to MDR.

Electrocoagulation in the treatment of industrial waters and wastewaters

Chemical coagulation is commonly used in raw water and wastewater treatment plants for the destabilisation of pollutants so that they can be removed in the subsequent separation processes. The most commonly used coagulation chemicals are aluminium and iron metal salts. Electrocoagulation technology has also been proposed for the treatment of raw waters and wastewaters. With this technology, metal cations are produced on the electrodes via electrolysis and these cations form various hydroxides in the water depending on the water pH. In addition to this main reaction, several side reactions, such as hydrogen bubble formation and the reduction of metals on cathodes, also take place in the cell. In this research, the applications of electrocoagulation were investigated in raw water treatment and wastewater applications. The surface water used in this research contained high concentrations of natural organic matter (NOM). The effect of the main parameters – current density, initial pH, electric charge per volume, temperature and electrolysis cell construction – on NOM removal were investigated. In the wastewater treatment studies, the removal of malodorous sulphides and toxic compounds from the wastewaters and debarking effluents were studied. Also, the main parameters of the treatment, such as initial pH and current density, were investigated. Aluminium electrodes were selected for the raw water treatment, whereas wastewaters and debarking effluent were treated with iron electrodes. According to results of this study, aluminium is more suitable electrode material for electrocoagulation applications because it produces Al(III) species. Metal ions and hydroxides produced by iron electrodes are less effective in the destabilisation of pollutants because iron electrodes produce more soluble and less charged Fe(II) species. However, Fe(II) can be effective in some special applications, such as sulphide removal. The resulting metal concentration is the main parameter affecting destabilisation of pollutants. Current density, treatment time, temperature and electrolysis cell construction affect the dissolution of electrodes and hence also the removal of pollutants. However, it seems that these parameters have minimal significance in the destabilization of the pollutants besides this effect (in the studied range of parameters). Initial pH and final pH have an effect on the dissolution of electrodes, but they also define what aluminium or iron species are formed in the solution and have an effect on the ζ-potential of all charged species in the solution. According to the results of this study, destabilisation mechanisms of pollutants by electrocoagulation and chemical coagulation are similar. Optimum DOC removal and low residual aluminium can be obtained simultaneously with electrocoagulation, which may be a significant benefit of electrocoagulation in surface water treatment compared to chemical coagulation. Surface water treatment with electrocoagulation can produce high quality water, which could be used as potable water or fresh water for industrial applications. In wastewater treatment applications, electrocoagulation can be used to precipitate malodorous sulphides to prevent their release into air. Technology seems to be able to remove some toxic pollutants from wastewater and could be used as pretreatment prior to treatment at a biological wastewater treatment plant. However, a thorough economic and ecological comparison of chemical coagulation and electrocoagulation is recommended, because these methods seem to be similar in pollutant destabilisation mechanisms, metal consumption and removal efficiency in most applications.

Studies on the Surface Properties and Catalytic Activity of Metal Chromites on Thermal Decomposition of Ammonium Perchlorate

Department of Applied Chemistry, Cochin University of Science and Technology

Acid-Base. Surface Electron Donatin6 &.Catai.Ytlc Properties Of Some Binary Mixed Oxides Containing Rare Earth Elements

Catalysis research underpins the science of modern chemical processing and fuel technologies. Catalysis is commercially one of the most important technologies in national economies. Solid state heterogeneous catalyst materials such as metal oxides and metal particles on ceramic oxide substrates are most common. They are typically used with commodity gases and liquid reactants. Selective oxidation catalysts of hydrocarbon feedstocks is the dominant process of converting them to key industrial chemicals, polymers and energy sources.[1] In the absence of a unique successfiil theory of heterogeneous catalysis, attempts are being made to correlate catalytic activity with some specific properties of the solid surface. Such correlations help to narrow down the search for a good catalyst for a given reaction. The heterogeneous catalytic performance of material depends on many factors such as [2] Crystal and surface structure of the catalyst. Thermodynamic stability of the catalyst and the reactant. Acid- base properties of the solid surface. Surface defect properties of the catalyst.Electronic and semiconducting properties and the band structure. Co-existence of dilferent types of ions or structures. Adsorption sites and adsorbed species such as oxygen.Preparation method of catalyst , surface area and nature of heat treatment. Molecular structure of the reactants. Many systematic investigations have been performed to correlate catalytic performances with the above mentioned properties. Many of these investigations remain isolated and further research is needed to bridge the gap in the present knowledge of the field.

Artificial neural network modeling for surface roughness prediction in cylindrical grinding of Al‐SiCp metal matrix composites and ANOVA analysis

Metal matrix composites (MMC) having aluminium (Al) in the matrix phase and silicon carbide particles (SiCp) in reinforcement phase, ie Al‐SiCp type MMC, have gained popularity in the re‐cent past. In this competitive age, manufacturing industries strive to produce superior quality products at reasonable price. This is possible by achieving higher productivity while performing machining at optimum combinations of process variables. The low weight and high strength MMC are found suitable for variety of components

Biennial Metal Discrepancy In The Surface Sediment Of Cochin Estuarine System

This study gave the first report on the biennial metal divergence in the sediments of Cochin Estuarine system (CES). Surface sediments from 6 prominent regions of CES were sampled in 2009 and 2011 for the geochemical and environmental assessment of trace metals (Cd, Co, Cr, Cu, Pb Fe, Mg, Mn, Ni and Zn).Besides texture, total organic carbon (TOC) and CHNS were also done. The contamination and risk assessment were performed by determining geochemical indices. Comparison with sediment quality guidelines were done to assess the probability for ecotoxicological threat to the estuary. Results showed that the measured heavy metals had varied spatial distribution patterns, indicating that they had complex origins and controlling factors

Model catalyst studies of the strong metal-support interaction: Surface structure identified by STM on Pd nanoparticles on TiO2(110)

Model catalysts of Pd nanoparticles and films on TiO2 (I 10) were fabricated by metal vapour deposition (MVD). Molecular beam measurements show that the particles are active for CO adsorption, with a global sticking probability of 0.25, but that they are deactivated by annealing above 600 K, an effect indicative of SMSI. The Pd nanoparticles are single crystals oriented with their (I 11) plane parallel to the surface plane of the titania. Analysis of the surface by atomic resolution STM shows that new structures have formed at the surface of the Pd nanoparticles and films after annealing above 800 K. There are only two structures, a zigzag arrangement and a much more complex "pinwheel" structure. The former has a unit cell containing 7 atoms, and the latter is a bigger unit cell containing 25 atoms. These new structures are due to an overlayer of titania that has appeared on the surface of the Pd nanoparticles after annealing, and it is proposed that the surface layer that causes the SMSI effect is a mixed alloy of Pd and Ti, with only two discrete ratios of atoms: Pd/Ti of 1: 1 (pinwheel) and 1:2 (zigzag). We propose that it is these structures that cause the SMSI effect. (c) 2005 Elsevier Inc. All rights reserved.

Hydrogen spillover on carbon-supported metal catalysts studied by inelastic neutron scattering. Surface vibrational states and hydrogen riding modes

Hydrogen spillover on carbon-supported precious metal catalysts has been investigated with inelastic neutron scattering (INS) spectroscopy. The aim, which was fully realized, was to identify spillover hydrogen on the carbon support. The inelastic neutron scattering spectra of Pt/C, Ru/C, and PtRu/C fuel cell catalysts dosed with hydrogen were determined in two sets of experiments: with the catalyst in the neutron beam and, using an annular cell, with carbon in the beam and catalyst pellets at the edge of the cell excluded from the beam. The vibrational modes observed in the INS spectra were assigned with reference to the INS of a polycyclic aromatic hydrocarbon, coronene, taken as a molecular model of a graphite layer, and with the aid of computational modeling. Two forms of spillover hydrogen were identified: H at edge sites of a graphite layer (formed after ambient dissociative chemisorption of H-2), and a weakly bound layer of mobile H atoms (formed by surface diffusion of H atoms after dissociative chernisorption of H-2 at 500 K). The INS spectra exhibited characteristic riding modes of H on carbon and on Pt or Ru. In these riding modes H atoms move in phase with vibrations of the carbon and metal lattices. The lattice modes are amplified by neutron scattering from the H atoms attached to lattice atoms. Uptake of hydrogen, and spillover, was greater for the Ru containing catalysts than for the Pt/C catalyst. The INS experiments have thus directly demonstrated H spillover to the carbon support of these metal catalysts.

Modelling metal cutting using modern ductile fracture mechanics: Quantitative explanations for some longstanding problems

The assumption that negligible work is involved in the formation of new surfaces in the machining of ductile metals, is re-examined in the light of both current Finite Element Method (FEM) simulations of cutting and modern ductile fracture mechanics. The work associated with separation criteria in FEM models is shown to be in the kJ/m2 range rather than the few J/m2 of the surface energy (surface tension) employed by Shaw in his pioneering study of 1954 following which consideration of surface work has been omitted from analyses of metal cutting. The much greater values of surface specific work are not surprising in terms of ductile fracture mechanics where kJ/m2 values of fracture toughness are typical of the ductile metals involved in machining studies. This paper shows that when even the simple Ernst–Merchant analysis is generalised to include significant surface work, many of the experimental observations for which traditional ‘plasticity and friction only’ analyses seem to have no quantitative explanation, are now given meaning. In particular, the primary shear plane angle φ becomes material-dependent. The experimental increase of φ up to a saturated level, as the uncut chip thickness is increased, is predicted. The positive intercepts found in plots of cutting force vs. depth of cut, and in plots of force resolved along the primary shear plane vs. area of shear plane, are shown to be measures of the specific surface work. It is demonstrated that neglect of these intercepts in cutting analyses is the reason why anomalously high values of shear yield stress are derived at those very small uncut chip thicknesses at which the so-called size effect becomes evident. The material toughness/strength ratio, combined with the depth of cut to form a non-dimensional parameter, is shown to control ductile cutting mechanics. The toughness/strength ratio of a given material will change with rate, temperature, and thermomechanical treatment and the influence of such changes, together with changes in depth of cut, on the character of machining is discussed. Strength or hardness alone is insufficient to describe machining. The failure of the Ernst–Merchant theory seems less to do with problems of uniqueness and the validity of minimum work, and more to do with the problem not being properly posed. The new analysis compares favourably and consistently with the wide body of experimental results available in the literature. Why considerable progress in the understanding of metal cutting has been achieved without reference to significant surface work is also discussed.

Simulated climate change impact on summer dissolved organic carbon release from peat and surface vegetation: implications for drinking water treatment

Uncertainty regarding changes in dissolved organic carbon (DOC) quantity and quality has created interest in managing peatlands for their ecosystem services such as drinking water provision. The evidence base for such interventions is, however, sometimes contradictory. We performed a laboratory climate manipulation using a factorial design on two dominant peatland vegetation types (Calluna vulgaris and Sphagnum Spp.) and a peat soil collected from a drinking water catchment in Exmoor National Park, UK. Temperature and rainfall were set to represent baseline and future conditions under the UKCP09 2080s high emissions scenario for July and August. DOC leachate then underwent standard water treatment of coagulation/flocculation before chlorination. C. vulgaris leached more DOC than Sphagnum Spp. (7.17 versus 3.00 mg g−1) with higher specific ultraviolet (SUVA) values and a greater sensitivity to climate, leaching more DOC under simulated future conditions. The peat soil leached less DOC (0.37 mg g−1) than the vegetation and was less sensitive to climate. Differences in coagulation removal efficiency between the DOC sources appears to be driven by relative solubilisation of protein-like DOC, observed through the fluorescence peak C/T. Post-coagulation only differences between vegetation types were detected for the regulated disinfection by-products (DBPs), suggesting climate change influence at this scale can be removed via coagulation. Our results suggest current biodiversity restoration programmes to encourage Sphagnum Spp. will result in lower DOC concentrations and SUVA values, particularly with warmer and drier summers.