Experimentally measured methane hydrate phase equilibria and ionic liquids inhibition performance in Qatar's seawater.

Qatar has the third-largest natural gas reserves in the world and is the second largest Liquefied natural gas (LNG) exporter in the world. These reserves are mainly located in its offshore North Field where the gas is extracted, transported to the onshore units, and is converted to LNG for international export. The formation of natural gas hydrates in the offshore subsea lines can cause unwanted blockages and hinder the smooth supply of gas supply from offshore to onshore units. In the present work, the formation and dissociation of methane gas hydrates have been studied in the ultra pure water system (UPW), artificial seawater (ASW), and Qatar seawater (QSW) at different conditions (4-10 MPa) using standard rocking cell rig. The naturally occurring seawater was collected from Ras Laffan seacoast located in Doha, Qatar. The seawater sample was examined for elemental analysis (SO4, Cl, Na, Ca, Mg, K, and Fe) using inductively coupled plasma atomic emission spectroscopy (ICP-AES) technique and its other properties like density, electrical conductivity, and pH were also measured. The experimental results show that the CH4 pure water HLVE curve is suppressed by about 3 K in Qatar seawater and 2 K in artificial seawater. The hydrate inhibition strength of the Ionic liquids (ILs) salts 3-Ethyl-1-methyl-1H-imidazol-3-ium methane-sulfonate [C7H14N2O3S] and 3-Ethyl-1-methyl-1H-imidazol-3-ium dicyanoazanide [C8H11N5] was evaluated in both the ultra pure water and Qatar seawater systems. Their performance was compared with methanol and other ILs salts reported in the literature. The selected ILs exhibited poor hydrate inhibition effect in the ultra pure water systems, but they show a noticeable thermodynamic and kinetic hydrate inhibition effect in the Qatar seawater system. The computational 3D molecular models of ILs and methanol were generated to cognize the plausible hydrate inhibition mechanism in the presence of these inhibitors.

Osmotic pressure estimation using the Pitzer equation for forward osmosis modelling.

Forward osmosis (FO) has received widespread recognition in the past decade due to its potential low energy production of water. This study presents a new model analysis for predicting the water flux in FO systems when inorganic-based draw solutions are used under variable experimental conditions for using a laboratory scale cross-flow single cell unit. The new model accounts for the adverse impact of concentration polarization (both ICP and ECP) incorporating the water activity by Pitzer to calculate the bulk osmotic pressures. Using the water activity provides a better correlation of experimental data than the classical van't Hoff equation. The nonlinear model also gave a better estimate for the structural parameter factor (S) of the membrane in its solution. Furthermore, the temperature and concentration of both the draw and feed solutions played a significant role in increasing the water flux, which could be interpreted in terms of the mass transfer coefficient representing ECP; a factor sensitive to the hydraulics of the system. The model provides greatly improved correlations for the experimental water fluxes.

Influence of composite particle formation on the performance and economics of grit removal.

Grit is routinely removed at the headworks of municipal wastewater treatment works to limit its onerous impact on downstream processes. Grit separation technologies are normally based on sedimentation of a homogeneous material (usually sand). However, in practice inorganic grit particles are likely to be combined with organic matter, such as fats oils and grease (FOG), producing a composite particle whose settling properties vary with the inorganic/organic content. A study of the impact of particle composition on its sedimentation has been conducted encompassing theoretical description (for particle settling in transitional flow), practical measurement and economic analysis. Practical measurement included sedimentation tests of homogeneous and composite particles along with characterisation of accumulated granular material sampled from actual municipal wastewater treatment works. The economic assessment was based on data from full-scale installations in the UK and US pertaining to remedial measures undertaken as a result of grit impacts, primarily accumulation in vessels and channels and damage of mechanical equipment through abrasion. Practical tests revealed coating of the sand grains with a FOG analogue (candlewax) to generate composite particles containing 45% wax by weight. The coated particles were then 30% less dense, 22% larger and 14% less settleable, on average, than the uncoated particles. Samples of accumulated grit taken from anaerobic digesters and aeration lanes from a full-scale plant indicated a FOG content (43%) similar to that of the waxed particles in the bench-scale tests, thus leading to a similar grain retardation of 14% assuming the FOG to be entirely associated with the grit. An assessment of the impact of the consequential breakthrough of grit particles due to buoyancy generated by composite particle formation indicated a $1.1 increase in operating costs per megalitre (ML) wastewater.

Adsorption characteristics of reactive dyes in columns of activated carbon.

Adsorption behaviour of reactive dyes in fixed-bed adsorber was evaluated in this work. The characteristics of mass transfer zone (MTZ), where adsorption in column occurs, were affected by carbon bed depth and influent dye concentration. The working lifetime (t(x)) of MTZ, the height of mass transfer zone (HMTZ), the rate of mass transfer zone (RMTZ), and the column capacity at exhaustion (q(column)) were estimated for the removal of remazol reactive yellow and remazol reactive black by carbon adsorber. The results showed that column capacity calculated at 90% of column exhaustion was lower than carbon capacity obtained from equilibrium studies. This indicated that the capacity of activated carbon was not fully utilized in the fixed-bed adsorber. The bed-depth service time model (BDST) was applied for analysis of reactive yellow adsorption in the column. The adsorption capacity of reactive yellow calculated at 50% breakthrough point (N(0)) was found to be 0.1 kg kg(-1) and this value is equivalent to about 14% of the available carbon capacity. The results of this study indicated the applicability of fixed-bed adsorber for removing remazol reactive yellow from solution.

Microcolumn studies of dye adsorption onto manganese oxides modified diatomite.

The method described here cannot fully replace the analysis of large columns by small test columns (microcolumns). The procedure, however, is suitable for speeding up the determination of adsorption parameters of dye onto the adsorbent and for speeding up the initial screening of a large adsorbent collection that can be tedious if a several adsorbents and adsorption conditions must be tested. The performance of methylene blue (MB), a basic dye, Cibacron reactive black (RB) and Cibacron reactive yellow (RY) was predicted in this way and the influence of initial dye concentration and other adsorption conditions on the adsorption behaviour were demonstrated. On the basis of the experimental results, it can be concluded that the adsorption of RY onto manganese oxides modified diatomite (MOMD) exhibited a characteristic "S" shape and can be simulated effectively by the Thomas model. It is shown that the adsorption capacity increased as the initial dye concentration increased. The increase in the dye uptake capacity with the increase of the adsorbent mass in the column was due to the increase in the surface area of adsorbent, which provided more binding sites for the adsorption. It is shown that the use of high flow rates reduced the time that RY in the solution is in contact with the MOMD, thus allowing less time for adsorption to occur, leading to an early breakthrough of RY. A rapid decrease in the column adsorption capacity with an increase in particle size with an average 56% reduction in capacity resulting from an increase in the particle size from 106-250 microm to 250-500 microm. The experimental data correlated well with calculated data using the Thomas equation and the bed depth-service time (BDST) equation. Therefore, it might be concluded that the Thomas equation and the BDST equations can produce accurate predication for variation of dye concentration, mass of the adsorbent, flow rate and particle size. In general, the values of adsorption isotherm capacity obtained in a batch system show the maximum values and are considerably higher than those obtained in a fixed-bed.

Thermodynamic behaviour and the effect of temperature on the removal of dyes from aqueous solution using modified diatomite: a kinetic study.

The effect of solution temperature and the determination of the thermodynamic parameters of adsorption of methylene blue (MB), Cibacron Reactive black C-NN (RB) and Cibacron Reactive golden yellow MI-2RN (RY) onto manganese-oxides-modified diatomite (MOMD), such as activation energy, E, enthalpy of activation, DeltaH*, entropy of activation, DeltaS*, and free energy of activation, DeltaG*, on the adsorption rates is important in understanding the adsorption mechanism. The rate and the transport/kinetic processes of dye adsorption onto the adsorbents were described by applying various kinetic adsorption models. This would lead to a better understanding of the mechanisms controlling the adsorption rate. The pseudo-second-order model was the best choice among all the kinetic models to describe the adsorption behaviour of RB onto MOMD, suggesting that the adsorption mechanism might be a chemisorption process. The activation energies, E, for RB, RY and MB were -6.74, 56.65 and 99.80 kJ/mol, respectively. The negative value of the activation energy suggested that the rise in the solution temperature did not favour RB adsorption onto MOMD. Moreover, the activation energy of the diffusion process, E', for RB, RY and MB increased as MB > RY >> RB. It means that the RB molecules are much faster moving and a lower energy is needed to diffuse into MOMD than RY and MB molecules. E', the activation energy for adsorption into pores, of RY is higher than E, indicating that the rate-limiting step of RY adsorption onto MOMD might be diffusion controlled, while the activation energy of the diffusion process, E', of MB is slightly lower than E, suggesting that the rate-limiting step is a combination of chemical and diffusion adsorption.

Effect of OH and silanol groups in the removal of dyes from aqueous solution using diatomite.

The removal of methylene blue, reactive black (C-NN), and reactive yellow (MI-2RN) from aqueous solution by calcined and raw diatomite at 980 degrees C was studied. These studies demonstrated the importance of the various functional groups on the mechanism of adsorption. The role of pore size distribution in the dye adsorption studies was also investigated. The adsorption isotherms were pH dependent. Henry and Freundlich adsorption isotherms were used to model the adsorption behavior and experimental results for all dyes used exhibited heterogeneous surface binding. The removal of the ionisable functional groups increased the pH(ZPC) value from 5.4 to 7.7, while FTIR, SEM and XRD analysis showed a remarkable decrease of the characteristic Si-OH peaks after calcinations at 980 degrees C. The removal of hydroxyl groups from the surface of diatomite lead to a decrease in the adsorption. It was evident from pH and infrared spectra results that mechanisms of methylene blue and reactive yellow adsorption differed from that of reactive black. Accordingly, adsorption on the external surface by n-pi interaction between the pi system of the RB and the electron lone pairs of the oxygen atoms of siloxane group and columbic attraction between the dye and the surface of calcined diatomite was proposed as a possible adsorption mechanism.

The effect of pH, temperature, and molecular size on the removal of dyes from textile effluent using manganese oxides-modified diatomite.

This work is an investigation on the use of manganese oxides-modified diatomite (MOMD) for the removal of color from textile wastewaters. The modification of the diatomite was carried out by treatment with manganese oxides; delta-bimessite type resulted. The surface area, pH(ZPC), Fourier transform infrared (FTIR), and scanning electron microscopy of MOMD were studied. The influence of concentration, pH, particle size, and temperature on the adsorption capacities of methylene blue (MB) and hydrolyzed reactive black (RB) and reactive yellow (RY) was investigated. Key thermodynamic parameters such as deltaH degrees, deltaS degrees, and deltaG degrees were also determined. The deltaH degrees of MB and hydrolyzed RB and RY was +94.64, -143.1, and -38.78 kJ/mol, respectively, whereas the deltaG degrees values of -17.68, -27.93, and -23.26 kJ/mol were obtained, indicating a spontaneous process with low activation-energy requirements. The findings further indicated that coulomb interaction, molecular size, and orientation of the dye and its surface charge played an important role in the adsorption and attachment of the dyes to the bimessite layers of MOMD.

The removal of dyes from textile wastewater: a study of the physical characteristics and adsorption mechanisms of diatomaceous earth.

The feasibility of using diatomite for the removal of the problematic reactive dyes as well as basic dyes from textile wastewater was investigated. Methylene blue, Cibacron reactive black and reactive yellow dyes were considered. Physical characteristics of diatomite such as pHsolution, pHZPC, surface area, Fourier transform infrared, and scanning electron microscopy were investigated. The surface area of diatomite was found to be 27.80 m2g(-1) and the pHZPC occurred around pH of 5.4. The results indicated that the surface charge of diatomite decreased as the pH of the solution increased with the maximum methylene blue removal from aqueous solution occurring at basic pH of around (10-11). Adsorption isotherms of diatomite with methylene blue, hydrolysed reactive black and yellow dyes were constructed at different pH values, initial dye concentrations and particle sizes. The experimental results were fitted to the Langmuir, Freundlich, and Henry models. The study indicated that electrostatic interactions play an important role in the adsorption of dyes onto diatomite. A model of the adsorption mechanism of methylene blue onto diatomite is proposed.

Sorption of lead ions on diatomite and manganese oxides modified diatomite.

Naturally occurring diatomaceous earth (diatomite) has been tested as a potential sorbent for Pb(II) ions. The intrinsic exchange properties were further improved by modification with manganese oxides. Modified adsorbent (referred to as Mn-diatomite) showed a higher tendency for adsorbing lead ions from solution at pH 4. The high performance exhibited by Mn-diatomite was attributed to increased surface area and higher negative surface charge after modification. Scanning electron microscope pictures revealed a birnessite structure of manganese oxides, which was featured by a plate-like-crystal structure. Diatomite filtration quality was improved after modification by manganese oxides. Good filtration qualities combined with high exchange capacity emphasised the potential use of Mn-diatomite in filtration systems.