A kinetic study on anaerobic reduction of sulphate, part II: incorporation of temperature effects in the kinetic model

The effects of temperature on the kinetics of anaerobic sulphate reduction were studied in continuous bioreactors using acetate as an electron donor. Across the range of temperatures applied from 20 to , the increasing of volumetric loading rate up to 0.08 to resulted in a linear increase in reduction rate of sulphate. The increasing reaction rate showed a lower dependence on volumetric loading rate in the range 0.1-. Further increase in volumetric loading rate above was accompanied by wash out of bacterial cells and a sharp decrease in reaction rate. Despite a similar pattern for dependency of reaction rate on volumetric loading at all temperatures tested, the magnitude of reaction rate was influenced by temperature, with a maximum rate of observed at . The effect of temperature on maximum specific growth rate (μ_max) and bacterial yield was insignificant. The values of maximum specific growth rate and yield were and 0.56-0.60 kg bacteria (), respectively. The decay coefficient (k_d) and apparent saturation constant () were both temperature dependent. The increase of temperature resulted in decreased values of , and higher values for k_d. Using the experimental data effect of temperature was incorporated in a kinetic model previously developed for anaerobic reduction of sulphate.     

A generalized analysis on material invariant characteristics for microwave heating of slabs

A generalized dimensionless formulation has been developed to predict the spatial distribution of microwave power and temperature. The ‘dimensionless analysis’ is mainly based on three numbers: wave number, ; free space wave number, ; and penetration number, , where is the ratio of sample thickness to wavelength of microwaves within a material, is based on wavelength within free space and is the ratio of sample thickness to penetration depth. The material dielectric properties and sample thicknesses form the basis of these dimensionless numbers. The volumetric heat source due to microwaves can be expressed as a combination of dimensionless numbers and electric field distributions. The spatial distributions of microwave power for uniform plane waves can be obtained from the combination of transmitted and reflected waves within a material. Microwave heating characteristics are obtained by solving energy balance equations where the dimensionless temperature is scaled with respect to incident microwave intensity. The generalized trends of microwave power absorption are illustrated via average power plots as a function of , and . The average power contours exhibit oscillatory behavior with corresponding to smaller for smaller values of . The spatial distributions of dimensionless electric fields and power are obtained for various and . The spatial resonance or maxima on microwave power is represented by zero phase difference between transmitted and reflected waves. It is observed that the number of spatial resonances increases with for smaller regimes whereas the spatial power follows the exponential decay law for higher regimes irrespective of and . These trends are observed for samples incident with microwaves at one face and both the faces. The heating characteristics are shown for various materials and generalized heating patterns are shown as functions of , and . The generalized heating characteristics involve either spatial temperature distributions or uniform temperature profiles based on both thermal parameters and dimensionless numbers ().     

Gas-liquid mass transfer in a circulating jet-loop nitrifying MBR

Based on airlift configuration, a novel circulating jet-loop submerged membrane bioreactor (JLMBR) adapted to ammonium partial oxidation has been developed. Membrane technology and combined air and water forced circulation are adopted to obtain a high biomass retention time and to achieve a separate control of mixing and aeration. This study is intended to determine how gas-liquid mass transfer is affected by operating conditions. In a first approximation, liquid was assumed to be perfectly mixed. A classical non-steady state clean water test, known as the “gas out-gas in” method, was used to determine the gas-liquid mass transfer coefficient k_La. Air and recirculated liquid superficial velocities were gradually increased from 0.013 to and 0.0056 to , respectively. Subsequently, the gas-liquid mass transfer coefficient k_La varied from 0.01 to . It appears to be influenced by the combined action of air and recirculated liquid flowrates in the range and , respectively, for air and liquid. Correlations are proposed to describe this double influence. Experiments were performed on tap water and a culture medium used for the autotrophic growth of nitrifying bacteria, respectively. Oxygen transfer appeared to be not significantly affected by the mineral salt encountered in this medium.     

The effect of magnetic fields on the electrodeposition of cobalt

The effect of a magnetic field on the electrodeposition of Co has been investigated with respect to the strength and the orientation of the magnetic field (B). Two different effects of the magnetic field B on the electrodeposition of cobalt have been observed. The first is the magnetohydrodynamic (MHD) effect caused by the Lorentz force (). The second is an effect due to the paramagnetic force (), caused by the concentration gradient () and therefore the gradient of the molar susceptibility (). The limiting current density and the deposition rate of Co increases if the B-field is oriented parallel to the electrode surface. This is mainly due to the expected convection induced by . Both, the Co deposition and the reduction of hydrogen ions, are affected by this. At high cathodic potentials the contribution of the hydrogen reduction to the process changed, which led to homogeneous deposits. A decreasing deposition rate was measured for B-fields oriented parallel or antiparallel to the flow of ions. These results are attributed to the effect of on the electrochemical processes close to the surface.     

Electrochemical performances of gel polymer electrolytes using tetra(ethylene glycol) diacrylate

A gel polymer electrolyte (GPE) was prepared using tetra(ethylene glycol) diacrylate monomer, benzoyl peroxide, and (). The LiCoO₂/GPE/graphite cells were prepared and their electrochemical properties were evaluated at various current densities and temperatures.The viscosity of the precursor containing the tetra(ethylene glycol) diacrylate monomer was around . The ionic conductivity of the gel polymer electrolyte at 20°C was around . The gel polymer electrolyte had good electrochemical stability up to vs. Li/Li⁺. The capacity of the LiCoO₂/GPE/graphite cell at rate was 63% of the discharge capacity at rate. The capacity of the cell at −10°C was 81% of the discharge capacity at 20°C. Discharge capacity of the cell with gel polymer electrolyte was stable with charge-discharge cycling.     

Synthesis, characterization and thermodynamic properties of poly(3-mesityl-2-hydroxypropyl methacrylate-co-N-vinyl-2-pyrrolidone)

Poly(3-mesityl-2-hydroxypropyl methacrylate-co-N-vinyl-2-pyrrolidone) P(MHPMA-co-VP) was synthesized in 1, 4-dioxane solution using benzoyl peroxide (BPO) as initiator at 60 °C. The copolymer was characterized by ¹H ¹³C NMR, FT-IR, DSC, TGA, size exclusion chromatography analysis (SEC) and elemental analysis techniques. According to SEC, the number-average molecular weight (M_n), weight-average molecular weight (M_w) and polydispersity index (PDI) values of PMHPMA-co-VP were found to be 58,000, 481,000 g/mol and 8.26, respectively. According to TGA, carbonaceous residue value of PMHPMA-co-VP was found to be 6% at 500 °C. Also, some thermodynamic properties of PMHPMA-co-VP such as the adsorption enthalpy, ΔH_a, molar evaporation enthalpy, ΔH_v, the sorption enthalpy, , sorption free energy, , sorption entropy, , the partial molar free energy, , the partial molar heat of mixing, , at infinite dilution was determined for the interactions of PMHPMA-co-VP with selected alcohols and alkanes by inverse gas chromatography (IGC) method in the temperature range of 323-463 K. According to the specific retention volumes, , the weight fraction activity coefficients of solute probes at infinite dilution, , and Flory-Huggins interaction parameters, between PMHPMA-co-VP-solvents were determined in 413-453 K. According to and , selected alcohols and alkanes were found to be non-solvent for PMHPMA-co-VP at 413-453 K. The glass transition temperature, T_g, of the PMHPMA-co-VP found to be 370 and 363 K, respectively, by IGC and DSC techniques, respectively.     

Hydrodynamic effects on the performance of an electrochemical reactor for destruction of copper cyanide—Part 1: in situ formation of the electrocatalytic film

An electrochemical reactor with stainless-steel electrodes was used for cyanide destruction and copper electrodeposition from dilute wastewater. With mechanical stirring, pumping or gas sparging, in situ deposition of a Cu oxyhydroxide film occurred on the anode at potentials vs. AgCl/Ag and had electrocatalytic properties for oxidation of cyanides. The Cu^II/Cu^I ratio in the electrocatalytic film was found to vary with the hydrodynamic conditions. The minimum mechanical energy dissipation, ranging from 1.5 to , necessary to create sufficient turbulence for film formation, was of a similar order of magnitude for all three means of transport enhancement. However, shear rates and shear stresses at the anode resulted in shearing of the film from the stainless-steel support.     

Temperature variations in the oxygen carrier particles during their reduction and oxidation in a chemical-looping combustion system

A particle reaction model including mass and heat transfer has been developed to know the temperature variations produced inside the oxygen carrier particles during the cyclic reduction and oxidation reactions taking place in a chemical-looping combustion (CLC) system. The reactions of the different oxygen carriers based on Cu, Co, Fe, Mn, and Ni during the reduction with fuel gas (CH₄, CO, and H₂) and oxidation (O₂) have been considered. In these systems, the oxidation reaction is always exothermic with subsequent heat release; however, the reduction reaction can be exothermic or endothermic depending on the metal oxide and the fuel gas. The heat generated inside the oxygen carriers during the exothermic reactions increases the particle temperature, and could affect the particle structure if the temperature increase is near to the melting point of the active materials. Several variables that affect the reaction rate and the heat transport process have been analyzed to know their effect on the internal particle temperature. For a given oxygen carrier and reaction, the maximum temperature of the particles depended mainly on the particle size, the reaction rate, and the external heat transfer resistance, being lower than the effect of the oxygen carrier porosity, type of inert material, and metal oxide content. The highest temperature variations were reached for the oxidation reactions, with the maximum corresponding to the Ni and Co oxygen carriers with values of for particles. The highest temperature increase observed during the reduction reactions corresponded to the reaction of CuO with CO, with values of for particles. For the rest of the reactions and metals, the variations in the particle temperature were below for particle sizes below . Under the typical operating conditions that exist in a CLC system, with particle sizes lower than , % of metal oxide content, and overall conversion times lower than , the increases of temperature with respect to the bulk conditions were lower than for any reaction of any oxygen carrier. Moreover, the temperature profiles inside the particles were near flat in most of the practical conditions, and no local points with high temperatures were found. Thus, changes in the solid porous structure of the carrier due to sintering during oxidation in fluidized bed reactors are not expected working at typical temperatures of CLC systems (1000-).     

Kinetics and equilibrium of dissolved oxygen adsorption on activated carbon

The macroscopic adsorption behavior of dissolved oxygen on a coconut shell-derived granular activated carbon has been studied in batch mode at 301 and 313 K for initial dissolved oxygen concentrations of 10-30 mg/l and oxygen/carbon ratios of 2-180 mg/g. BET (Brunauer, Emmett, and Teller) surface area, micropore volume, and pore size distribution were determined from N₂ isotherm data for fresh and used samples of carbon. The surface groups were characterized using Boehm titrations, potentiometric titrations, and FTIR study. The material is characterized by its high specific surface area , microporocity (micropore volume ), its basic character ( total basic groups) and its high iron content (15,480 ppm Fe). BET n-layer isotherm describes adsorption equilibrium suggesting cooperative adsorption and important adsorbate-adsorbate interactions. Kinetic data suggest a process dependent on surface coverage. At low coverage a Fickian, intraparticle diffusion rate model assuming a local equilibrium isotherm (oxygen dissociation reaction) adequately describes the process. The calculated diffusion coefficients (D) vary between and for initial oxygen concentration of 10 and 20 mg/l, respectively. Sensitivity analysis shows that the oxygen dissociation equilibrium constant determines the equilibrium concentration, whereas the diffusion coefficient controls the kinetic rate of the adsorption process having no effect at the final equilibrium concentration. A combined kinetic mass transfer model with concentration-dependent diffusion (parabolic form) has been developed and successfully applied on the dissolved oxygen adsorption system at high surface coverage. For equilibrium uptake of the estimated mean mass transfer coefficient and adsorption rate constant are and , respectively.