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.     

The effect of bubble column diameter on gas holdup in fiber suspensions

Three bubble column diameters (D=10.2, 15.2, and 32.1 cm) are employed to study the scale-up effect on gas holdup in air-water and air-water-cellulose fiber (hardwood, softwood, and BCTMP) systems. The effect of column diameter depends on flow regime and fiber mass fraction. When , gas holdup decreases with increasing column diameter for the transitional and heterogeneous flow regime, and column diameter effects are negligible in the homogeneous flow regime. When , gas holdup is only affected by column diameter in the transitional flow regime for an air-water system and low fiber mass fraction suspensions (C?0.25%); column diameter effects disappear at medium fiber mass fractions (e.g., C=0.8%) but are significant at high fiber mass fractions (e.g., C=1.4%).     

Carbon dioxide absorption with aqueous potassium carbonate promoted by piperazine

Many commercial processes for the removal of carbon dioxide from high-pressure gases use aqueous potassium carbonate systems promoted by secondary amines. This paper presents thermodynamic and kinetic data for aqueous potassium carbonate promoted by piperazine. Research has been performed at typical absorber conditions for the removal of CO₂ from flue gas.Piperazine, used as an additive in 20- potassium carbonate, was investigated in a wetted-wall column using a concentration of at 40-80°C. The addition of piperazine to a potassium carbonate system decreases the CO₂ equilibrium partial pressure by approximately 85% at intermediate CO₂ loading. The distribution of piperazine species in the solution was determined by proton NMR. Using the speciation data and relevant equilibrium constants, a model was developed to predict system speciation and equilibrium.The addition of piperazine to potassium carbonate increases the rate of CO₂ absorption by an order of magnitude at 60°C. The rate of CO₂ absorption in the promoted solution compares favorably to that of MEA. The addition of piperazine to potassium carbonate increases the heat of absorption from 3.7 to . The capacity ranges from 0.4 to for PZ/K₂CO₃ solutions, comparing favorably with other amines.     

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.     

Gas-solid adsorption of selected volatile organic compounds on titanium dioxide Degussa P25

This paper focuses on the adsorption of gaseous trichloroethylene, toluene and chlorobenzene on the photocatalyst TiO₂ Degussa P25. An optimized EPICS (Equilibrium Partitioning In Closed Systems) methodology was used to study equilibrium partitioning. For the three compounds investigated, equilibrium adsorption was reached within of incubation. Adsorption isotherms, determined at a temperature (T) of and relative humidities (RH) of 0.0% and 57.8% were found to be linear (R²>0.993,n=5), indicating that no monolayer surface coverage was reached in the concentration interval studied ). Within the linear part of the isotherm, the influence of both relative humidity and temperature was investigated in a systematic way and discussed from a thermodynamic point of view. Data analysis resulted in a double linear regression for 22% ?RH?90% and . The equilibrium adsorption coefficient represents the equilibrium concentration ratio and ΔU_ads is the internal energy of adsorption . At RH=0.0%, experimental K values were a factor 5-10 higher than those expected from the regression equation, indicating that another adsorption mechanism becomes important below monolayer surface coverage of TiO₂ by water vapour molecules. Since surface interactions are of primary importance in photocatalytic reactions, this paper contributes to a better understanding of the basic mechanisms of TiO₂ mediated heterogeneous photocatalysis and is an interesting tool for developing optimized mathematical models.     

Flow behavior and regime transition in a high-density circulating fluidized bed riser

Flow behavior and flow regime transitions were determined in a circulating fluidized bed riser (0.203 m i.d. × 5.9 m high) of FCC particles (, ). A momentum probe was used to measure radial profiles of solids momentum flux at several heights and to distinguish between local net upward and downward flow. In the experimental range covered (; ), the fast fluidization flow regime was observed to coexist with dense suspension upflow (DSU). At a constant gas velocity, net downflow of solids near the wall disappeared towards the bottom of the riser with increasing solids mass flux, with dense suspension upflow achieved where there was no refluxing of solids near the riser wall on a time-average basis. The transition to DSU conditions could be distinguished by means of variations of net solids flow direction at the wall, annulus thickness approaching zero and flattening of the solids holdup versus G_s trend. A new flow regime map is proposed distinguishing the fast fluidization, DSU and dilute pneumatic transport flow regimes.     

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.     

Anomalous IR optical properties of aggregates of Pd nanoparticles induced through electrochemical cyclic voltammetry

IR optical properties of Pd nanoparticles with different size and aggregation state were studied in the current paper. The dispersed Pd nanoparticles () stabilized with poly(N-vinylpyrrolidone) (PVP) were synthesized by the seeding growth method, in which the seeds were formed step by step through reducing H₂PdCl₄ with ethanol. The dispersed Pd nanoparticles of much large size () were grown from the by keeping the colloid of undisturbed for 150 days at room temperature around 20 °C. The aggregates of () were prepared through an agglomeration process induced during a potential cyclic scanning between −0.25 V and 1.25 V for 20 min at a scan rate of 50 mV s⁻¹. Scanning electron microscope (SEM) patterns confirmed such aggregation of . Fourier transform infrared (FTIR) spectroscopy together with CO adsorption as probe reaction was employed in studies of IR optical properties of the prepared Pd nanoparticles. The results demonstrated that CO adsorbed on films substrated on CaF₂ IR window or glassy carbon (GC) electrode yielded two strong IR absorption bands around 1970 cm⁻¹ and 1910 cm⁻¹, which were assigned to IR absorption of CO bonded on asymmetric and symmetric bridge sites, respectively. Similar IR bands were observed in spectra of CO adsorbed on films, except the IR bands were much weak, whereas CO adsorbed on film produced an IR absorption band near 1906 cm⁻¹, and an anomalous IR absorption band whose direction has been completely inverted around 1956 cm⁻¹. The direction inversion of the IR band of CO bonded to asymmetric bridge sites on was ascribed to the interaction between Pd nanoparticles inside the aggregates. Based on FTIR spectroscopic and cyclic voltammetric results, the aggregation mechanism of Pd nanoparticles from to has been suggested that the agglomeration of Pd nanoparticles was driven by the alteration of electric field across electrode-electrolyte interface, when the PVP stabilizer was stripped via oxidation during cyclic voltammetry.     

Exothermic oxidations in supercritical CO2: effects of pressure-tunable heat capacity on adiabatic temperature rise and parametric sensitivity

Many oxidation reactions, including H₂ combustion with O₂, have been shown to admit the phenomenon of parametric sensitivity. Given its inertness to oxidation and non-flammable nature, supercritical CO₂ (scCO₂) is a desirable solvent for performing oxidations. Further, for oxidations that employ H₂O₂ as an oxidant, the use of scCO₂ as a solvent has been suggested for producing H₂O₂ in situ by reacting H₂ and O₂. Another significant, and as yet not fully understood, advantage of using scCO₂ is the ability to exploit its liquid-like heat capacity, which exhibits a maximum in the near-critical region (1.01-1.2T_c and 0.9-2.0P_c). It is shown in this modeling study that by performing an oxidation reaction in scCO₂, the temperature rise accompanying the highly exothermic reaction can be effectively controlled. To demonstrate this concept, we simulated the maximum temperature rise (ΔT_ad) for H₂ combustion with O₂ in CO₂ in a constant-pressure adiabatic reactor, at feed temperatures ranging from 300 to and reactor pressures from 1 to . At a feed temperature of , a five-fold reduction in ΔT_ad value (from 209 to ) is predicted by tuning the operating pressure from 1 to . In contrast, the ΔT_ad in N₂ medium is relatively insensitive in the 1- pressure range and is six times greater (roughly ) compared to the value predicted with CO₂ medium at . Further, the values of β (the dimensionless temperature rise parameter) may also be sensitively tuned with pressure in the near-critical region such that parametric sensitivity is minimized. These results indicate that the liquid-like heat capacities of scCO₂ may be exploited to control the adiabatic temperature rise and to ameliorate parametric sensitivity during exothermic reactions, a problem of fundamental and practical significance.     

Dispersion mechanism of nano-particulate aggregates using a high pressure wet-type jet mill

A high pressure wet-type jet mill was employed to disperse nano-particle suspensions. Commercially available nano-particles, fumed silica (SiO₂) of primary particle diameter (d₀) ranging from 7 to 40 nm, alumina (Al₂O₃) of and titanium oxide (TiO₂) of were dispersed in the continuous phase up to viscosity . Ion exchanged water, aqueous ethylene glycol and aqueous polyethylene glycol solutions with molecular weight up to 2 000 000, were used as the continuous phase. Particle size distribution, zeta potential and suspension viscosity were measured under a wide range of process conditions. The smaller the d₀ was, the harder it was to disperse the aggregates. Zeta potential was largely dependent on d₀ at any process conditions and became dependent on η_c for . The energy barrier was evaluated by taking van der Waals attractive forces, electrostatic repulsive forces and dispersive forces into consideration. Cavitation measurements showed a negligible cavitation during the passage through the jet mill; therefore aggregate disruption was modeled for fully turbulent flow. Aggregate disruption occurred in inertia sub-range for and in viscous sub-range for . By balancing mechanical energy with turbulent disruptive energy, a mechanistic model was developed for each sub-range. The analysis of fractal dimensionality showed that nano-aggregates were made up by particle-particle collision in inertia sub-range and orthokinetic cluster-cluster collision in viscous sub-range. The rheological data obtained were expressed according to a modified Casson model.