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 ().     

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.     

Oxidation kinetics of Iron(II) complexes of trans-1,2-diaminocyclohexanetetraacetate (cdta) with dissolved oxygen: Reaction mechanism, parameters of activation and kinetic salt effects

The present investigation takes concern about a spiny environmental problem afflicting the pulp mill industry exploiting the Kraft sulfate-pulp process where dilute total reduced sulfur contaminants are co-mixed with oxygen in large-volume gas effluents. A potential Redox process for removing the total reduced sulfurs consists in oxidizing them by means of iron(III) organometallic complexes while the co-mixed oxygen mediates the oxidative regeneration of iron(II) into iron(III) complexes. In this work, the oxidation kinetics of iron(II) trans-1,2,-diaminocyclohexanetetraacetate (cdta) complexes with molecular oxygen (O₂) as the source oxidant was investigated for a wide pH range (1.75<pH<12) in a 3.2 dm³ single-phase stirred cell reactor within the [281-323 K] temperature range. Simultaneous measurements of iron(II)-cdta (50-) and O₂ (0.5-) were used to clarify the reaction mechanism which has been interpreted differently in previous works. The observed kinetic data in alkaline solutions could be accounted for in terms of three forward [Fe²⁺cdta^4-+O₂ (rate-limiting, k_1,app), , 2Fe²⁺cdta^4-+H₂O₂] and one reverse [ (k_-1,app,n=0 or 1)] elementary steps. Assessment of the rate-limiting apparent rate constant led to the following results ( at and , , ). Fe³⁺OH^-cdta^4-, being the dominating iron(III) product at pH>10, was found to be less reactive than Fe³⁺cdta^4- with the superoxide intermediate , thus reducing the effect of the reverse step at higher pH. A study on the effect of electrolytes on the reaction rate led to the conclusion that salts increase the rate constant k_1,app. Finally, kinetic results in acidic conditions leading to the formation of other iron(II)-cdta complexes (i.e., Fe²⁺cdta^4-H⁺) and another superoxide intermediates are reported and discussed.     

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.     

Sonocrystallisation of sodium chloride particles for inhalation

Fine sodium chloride particles are of pharmaceutical interest in aerosol delivery for diagnosis of asthma and bronchial related disorders. In this paper, stable NaCl particles with size ranging from approximately to sub-micron range were achieved by sonocrystallisation. The effects of sonocrystallisation temperature, ultrasonic power output and salt concentration were investigated in the ranges of , 22-60 W and 8-34 g/100 g water, respectively, under a fixed ultrasonic frequency of 20 kHz. Size and morphology characterisation of particles were undertaken using laser diffraction and scanning electron microscopy. Optimally prepared particles were spray dried followed by in vitro impaction test for inhalation efficiency determination using an Aeroliser^®. Optimal conditions of temperature ), ultrasonic power output and salt concentration water) exist that reduced the size of the crystals to the sub-micron scale. Spray drying increased the size of the prepared particles and altered the cubic shape to more rounded morphology. The fine particle fraction (based on recovery) was improved from approximately 12 to 34% when dispersion air flow rate was increased from 60 to 120 L/min. Sonocrystallisation represents an effective method for the preparation of NaCl particles suitable for pharmaceutical inhalation. The main advantage of this method is that it is rapid, simple and produces small crystal NaCl particles suitable for inhalation.     

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.     

Kinetics of water sorption on SWS-1L (calcium chloride confined to mesoporous silica gel): Influence of grain size and temperature

Kinetics of water sorption on loose grains of composite sorbent CaCl₂ confined to mesoporous silica (SWS-1L) was measured at and over water uptake range 0-0.47 g/g for various particle sizes R_p (between 0.355 and 1.4 mm). The measurements were performed in a constant pressure unit based on a CAHN microbalance under isothermal external conditions.The results obtained evidence an enhancement of the sorption rate and apparent diffusion constant with the decrease in the particle size (approximately as at ). Contribution of thermal effects was found for water sorption on smaller SWS particles (0.355-0.425 mm), which decreases the sorption rate.The apparent water diffusivity was found to depend on the local slope of the SWS water sorption isotherm. The pore diffusivity of water in the temperature range 33-69 °C was calculated from experimental data that is approximately 10 times lower than the Knudsen pore diffusivity estimated for pores of silica KSK. The possible reasons of the diffusivity reduction are discussed.     

Fluidization behavior in a circulating slugging fluidized bed reactor. Part II: Plug characteristics

In the transporting square nosed slugging fluidization regime () a bed of polyethylene powder with a low density () and a large particle size distribution () was operated in two circulating fluidized bed systems (riser diameters 0.044 and 0.105 m). A relation was derived for the plug velocity as a function of the gas velocity, solids flux, riser diameter, particle size range and particle and powder properties. The influence of the plug length on the plug velocity, the raining rate of solids onto and from the plugs and the influence of the particle size range on the plug velocity is accounted for.     

Chain length dependent termination in radical cross-linking polymerization

The work presents an evidence in support of chain length dependent termination during cross-linking polymerization. It is based on the behavior of the ratio of the bimolecular termination coefficient to propagation rate coefficient k_p during the after-effect of a photo-induced polymerization. The chain-length dependence was manifested by a decrease of the ratio with the increase in dark reaction time faster than that resulting from the conversion increase. Two monomethacrylate/dimethacrylate and one dimethacrylate/dimethacrylate systems were chosen, which enabled to study the chain-length dependence as a function of cross-link density of the polymer being formed and physical properties of the initial composition. The ratios of the polymerization rate coefficients were calculated for various postpolymerization processes as a function of dark reaction conversion using the mixed termination model (concerning the bimolecular and monomolecular termination occurring parallel). A rapid drop of the ratio during the dark reaction was observed at the beginning of the after-effect and in slightly cross-linked systems suggesting a significant chain length dependence, but when the cross-link density increased with conversion or with cross-linking agent concentration in the feed, the drop of the ratio became much slower indicating that the chain length dependence decreased.     

Mechanism of enhanced gas absorption in presence of fine solid particles. Effect of molecular diffusivity on mass transfer coefficient in stirred cell

Desorption of oxygen and hydrogen from various liquids (water, 0.8 molar sodium sulphate solution) containing suspended particles of activated carbon at various solid loading was investigated. The desorption was used to avoid supersaturation effect which was observed during oxygen and hydrogen absorption into liquid saturated with nitrogen. Experiments were carried out in a stirred cell with flat gas-liquid interface at and atmospheric pressure. An increase of k_L upon addition of the particles was observed. Enhancement factor increases with increasing contact time of the particles with liquid reaching maximum steady-state value of approx. 3 after sufficiently long time (a few hours) regardless of solid loading , agitator frequency and solute gas (O₂,H₂). The results fit the correlation (e is specific power dissipated by agitator in liquid and D is molecular diffusivity of gas absorbed) with the exponent for liquids without and for the liquids with the particles. It indicates that the interface is rigid in absence of particles and hinders the motion of liquid along the interface forming boundary layer while in the presence of particles the interface is completely mobile and surface renewal proceeds according to the penetration model. These results confirm a finding of Kaya and Schumpe (2005) that the enhancement of mass transfer in the cell at the presence of hydrophobic solids is due to clean-up of the interface from surfactants by their adsorption on hydrophobic solids rather than by a “shuttle mechanism” exerted by particles with a high adsorption capacity for the transfer component.     

Macroscopic investigation of hydrate film growth at the hydrocarbon/water interface

Clathrate hydrate film growth has been investigated at the hydrocarbon/water interface for cyclopentane and methane hydrate, using video microscopy combined with gas consumption measurements. Hydrate formation was characterized by the film thickness, propagation rate across the hydrocarbon/water interface, and gas consumption. The film formation processes of cyclopentane and methane hydrate were measured over the temperature range of 260-273 K and pressure range of atmospheric to 8.3 MPa. Hydrate formation was initiated by the propagation of a thin, porous film across the hydrocarbon/water interface. This thickening rate was strongly dependent on the hydrate former solubility in the aqueous phase, in the absence and presence of hydrate. The methane hydrate film thickness began at about and grew to a final thickness (20-) which increased with subcooling. The cyclopentane hydrate film thickness began at about and grew to a final thickness (15-) which again increased with subcooling. The hydrate film grew into the water phase. Gas consumption indicated that the aqueous phase supplied hydrate former during the initial hydrate growth, and the free gas supplied the hydrate former for film thickening.