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.     

Structure, dissolution, and passivation of Ni(111) electrodes in sulfuric acid solution: an in situ STM, X-ray scattering, and electrochemical study

Results of a detailed study of Ni(111) surfaces in air and in sulfuric acid solution (pH 1.0-2.7) by a combination of STM, surface X-ray scattering using synchrotron radiation, and electrochemical techniques are presented. Ni(111) samples, prepared via annealing in H₂ and exposure to air at room temperature, are covered by a smooth three to four layers thick NiO(111) film with parallel (NiO[]∣∣Ni[]) and anti-parallel (NiO[]∣∣Ni[]) in-plane orientation. Electrochemical reduction at potentials ≤−0.40 V_Ag/AgCl results in the formation of a well-defined, oxide-free surface with large terraces, a low surface mobility, and a (1×1) lattice on the atomic scale. X-ray reflectivity data indicate vertical lattice expansion for the topmost Ni layer and a strongly bound sulfate or oxygen species. Active Ni dissolution commences at potentials ≥−0.25 V_Ag/AgCl by a step-flow mechanism, followed by the rapid formation of large three-dimensional etch pits, leading to considerable surface roughening. In situ STM observations of the passive film formation show at potentials ≥−0.10 V_Ag/AgCl the nucleation and growth of an initial ‘grainy’ phase, which is attributed to a Ni hydroxide, followed by a slower restructuring process. According to our combined STM and SXS data, the resulting steady-state passive film exhibits a duplex structure, with a crystalline, inner NiO(111) layer, consisting of exclusively anti-parallel oriented grains (NiO[]∣∣Ni[]) which are slightly tilted relative to the substrate lattice, and a porous, probably amorphous hydroxide phase on top. The thickness of the crystalline NiO film increases with potential by 14-17 Å V⁻¹. In addition, structural changes of the oxide film during immersion of Ni samples into the sulfuric acid solution at potentials in the passive range and after emersion from the electrolyte were observed, which indicate the slow conversion of the air-formed into the passive oxide and the (partial) reformation of the air-formed oxide, respectively.     

Correction of the secondary flow effect for binary diffusion coefficients using coated/uncoated diffusion columns

To determine binary diffusion coefficients from tracer response measurements with a coiled capillary column (curved tube) at relatively high flow rates, a conversion formula to correct for the secondary flow effect was derived from the second central moment of the impulse response curve. Its practical expression was obtained analytically by the perturbation method up to λ¹⁰, where λ is the ratio of the tube radius to the coil radius. The reliability of the correction was evaluated by an alternative series of λ. As a result, the effective range of DeSc^1/2<8-9.5 without correction widened to DeSc^1/2<18-19 to determine the diffusion coefficient within 1% error. Applicability of the correction was demonstrated for phenol and ubiquinone CoQ10 using a coated column, and for benzene using an uncoated column (the Taylor dispersion), in supercritical carbon dioxide at 16- and .     

Physical modelling and similitude of air bubble entrainment at vertical circular plunging jets

When a plunging jet impinges into a pool of liquid, air bubble entrainment takes place if the inflow velocity exceeds a threshold velocity. This study investigates air entrainment and bubble dispersion in the developing flow region of vertical circular plunging jets. Three scale models were used and detailed air-water measurements (void fraction, bubble count rate, bubble sizes) were performed systematically for identical inflow Froude numbers. The results highlight that the modelling of plunging jet based upon a Froude similitude is affected by significant scale effects when the approach flow conditions satisfied We₁<1E+3, while some lesser scale effect was noticed for V₁/u_r<10 and We₁>1E+3. Bubble chord time measurements showed pseudo-chord sizes of entrained bubbles ranging from less than to more than with an average pseudo-chord size were between 4 and . However, bubble size data could not be scaled properly.     

Oxidation of FGD-CaSO3 and effect on soil chemical properties when applied to the soil surface

Use of high-sulfur coal for power generation in the United States requires the removal of sulfur dioxide (SO₂) produced during burning in order to meet clean air regulations. If SO₂ is removed from the flue gas using a wet scrubber without forced air oxidation, much of the S product created will be sulfite (). Plants take up S in the form of sulfate (). Sulfite may cause damage to plant roots, especially in acid soils. For agricultural uses, it is thought that in flue gas desulfurization (FGD) products must first oxidize to in soils before crops are planted. However, there is little information about the oxidation of in FGD product to under field conditions. An FGD-CaSO₃ was applied at rates of 0, 1.12, and 3.36 Mg ha⁻¹ to the surface of an agricultural soil (Wooster silt loam, Oxyaquic Fragiudalf). The in the surface soil (0-10 cm) was analyzed on days 3, 7, 17, 45, and 61. The distribution of and Ca in the 0-90 cm soil layer was also determined on day 61. Results indicated that in the FGD-CaSO₃ rapidly oxidized to on the field surface during the first week and much of the and Ca moved downward into the 0-50 cm soil layer during the experimental period of two months. It is safe to grow plants in soil treated with FGD-CaSO₃ if the application is made at least three days to several weeks before planting.     

A mechanism study of chloride and sulfate effects on Hg reduction in sulfite solution

This paper studied the effects of sulfate and chloride ions on bivalent mercury (Hg²⁺) absorption and reduction behaviors in a simulated WFGD system. The aqueous mercuric ion-sulfite system reduction behaviors were monitored and investigated using a UV-visible spectrum. Thereafter, the mechanism of Hg²⁺ reduction in the presence of sulfate and chloride ions was proposed. Experimental results revealed that both sulfate and chloride ions had inhibition effects on aqueous Hg²⁺ reduction to Hg⁰. The inhibition was assumed due to the formation of (in the presence of ) and / (in the presence of Cl⁻). And it was found that complex was more stable than in excess of Cl⁻. The formation of the above-mentioned complexes in the presence of and Cl⁻ would damp the formation of HgSO₃, whose decomposition was assumed to be the key step of Hg²⁺ reduction.     

Observation and modelling of capillary flow occlusion resulting from the capture of superparamagnetic nanoparticles in a magnetic field

The magnetic field mediated capture of 10 nm diameter superparamagnetic nanoparticles, in the form of agglomerates of mean diameter 330 and 580 nm, from microcapillary flows has been observed and modelled. The steady state thickness of the captured layer in microcapillaries of diameter 400- could be predicted for both the 330 and the 580 nm diameter agglomerates at flow rates of between 0.1 and . The model provides insight into blockage formation at a constant flow rate as a precursor to the prediction of thrombotic embolism in magnetic directed therapies. Capillary constriction was particularly acute for the 580 nm agglomerates in large microcapillaries with flow rates of . From this model, agglomerates of diameter 330 nm or less offer the potential for minimal microcapillary occlusion in a range of flow rates.     

Axial dispersion of particles in a slugging column—the role of the laminar wake of the bubbles

Axial solid dispersion promoted by Taylor bubbles in a batch liquid column was studied. A mechanistic model was developed to predict the axial solid dispersion. The model is based on the upward transport of particles inside closed wakes of non-interacting Taylor bubbles. The model predictions are compared with experimental data. The experimental data were obtained in a test tube of internal diameter. The particle volumetric distribution was measured by several differential pressure transducers placed along the column. Two classes of glass beads, mean diameter 180 and , were suspended in aqueous glycerol solutions, with glycerol percentage ranging from 40% (v/v) to 100% (v/v). The amount of particles in the column was such that the volumetric particle fractions were 0.1, 0.2 and 0.3, supposing homogeneous liquid-solid suspension. The air flow rate ranged from 90×10⁻⁶ to at PTN conditions. The obtained experimental data are in good agreement with the model predictions for laminar wakes, i.e., closed wakes with internal recirculation and without vortex shedding. The experimental data show a higher upward particle transport for wakes in the transition laminar-turbulent regime; closed wakes with internal recirculation and vortex shedding. The upward particle transport is higher for increasing air flow rate, decreasing particle diameter and increasing amount of particles in the column.     

Investigation on diffusion behavior of Li in LiFePO4 by capacity intermittent titration technique (CITT)

Capacity intermittent titration technique (CITT) was used to investigate the chemical diffusion coefficient () of lithium-ion in LiFePO₄ cathode material. The values of at the galvano-charge current of 0.2 and 0.4 mA were respectively found to range from 8.8 × 10⁻¹⁶ to 8.9 × 10⁻¹⁴ cm² s⁻¹ and from 1.2 × 10⁻¹⁶ to 8.5 × 10⁻¹⁴ cm² s⁻¹ in the voltage range from 3.2 to 4 V (vs. Li⁺/Li). The transfer coefficients of cathode (0.32-0.42) and anodic (0.26-0.3), and the standard rate constant (1.58 × 10⁻⁹ to 1.30 × 10⁻⁸ cm s⁻¹) were measured from the Tafel plots of LiFePO₄ in the equilibrium potential range from 3.06 to 3.45 V. From these kinetic parameters, the finite kinetics at interface was taken into account to revise the above values of . The revised values of at the galvano-charge current of 0.2 and 0.4 mA were respectively found to range from 2.44 × 10⁻¹⁵ to 2.21 × 10⁻¹³ cm² s⁻¹ and from 5.81 × 10⁻¹⁶ to 3.22 × 10⁻¹³ cm² s⁻¹ in the voltage range from 3.2 to 4 V. Results show that the approximation of infinite charge-transfer kinetics leads to a spurious value of which is lower than the revised value, and the spurious extent depends on the galvano-charge current of CITT experiment.     

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.     

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.     

Electroreduction of peroxycitric acid coexisting with hydrogen peroxide in aqueous solution

The electrochemical reduction of peroxycitric acid (PCA) coexisting with citric acid and hydrogen peroxide (H₂O₂) in the equilibrium mixture was extensively studied at a gold electrode in acetate buffer solutions containing 0.1 M Na₂SO₄ (pH 2.0-6.0) using cyclic and hydrodynamic voltammetric, and hydrodynamic chronocoulometric measurements. The reduction of PCA was characterized to be an irreversible, diffusion-controlled process, and the cyclic voltammetric reduction peak potential () was found to be more positive by ca. 1.0 V than that of the coexisting H₂O₂, e.g., the values obtained at 0.1 V s⁻¹ for PCA and H₂O₂ were 0.35 and −0.35 V, respectively, vs. Ag|AgCl|KCl (sat.) at pH 3.3. The of PCA was found to depend on pH, i.e., at pH > 4.5, the plot of vs. pH gave the slope (−64 mV decade⁻¹) which is close to the theoretical value (−59 mV decade⁻¹) for an electrode process involving the equal number of electron and proton in the rate-determining step, while at pH < 4.5, the was almost independent of pH. The relevant electrochemical parameters, Tafel slope, number of electrons, formal potential (E⁰′), cathodic transfer coefficient and standard heterogeneous rate constant (k⁰′) for the reduction of PCA and the diffusion coefficient of PCA were determined to be ca. 100 mV decade⁻¹, 2, 1.53 V (at pH 2.6), 0.29, 1.2 × 10⁻¹² cm s⁻¹ and 0.29 × 10⁻⁵ cm² s⁻¹, respectively, and except for E⁰′, the obtained values were almost independent of the solution pH. The overall mechanism of the reduction of PCA was discussed.     

High strength wastewater treatment in a jet loop membrane bioreactor: kinetics and performance evaluation

Treatment of wastewater containing high organic matter was investigated by means of a jet loop bioreactor combined with a membrane process. Volume of jet loop bioreactor and area of membrane filtration unit were 23 l and 155 cm² respectively. It was found that jet loop reactor had high mass transfer coefficient (K_La) varying from 58.8 to 486 h^-1 depending on the water flow rate (i.e. power input) and air flow rate. Oxygen transfer efficiency and oxygenation capacity of the reactor varied from 12 to 22.5% and from 0.2 to 1.8 , respectively. The efficiency of jet loop membrane bioreactor was found to be approximately 97% for a volumetric organic load of 2- over a period of 10 weeks. The reactor was not disturbed from the organic loads up to , but the treatment efficiency decreased to about 60% at higher organic loads. This decrease was due to insufficient oxygen transfer rate. The relationship between the effluent substrate concentration and the specific oxygen uptake rate (SOUR) values was determined. Applied food/microorganism (F/M) ratio was varied between 2.5 and . Critical sludge age of the system () was evaluated to be 7.2 h. Sludge with unsatisfactory settling characteristics formed at high F/M values under turbulent conditions. Therefore, membrane process was used for solid-liquid separation and effluent solid concentration was approximately zero. Specific cake resistances (α) changed with F/M ratio. It was found that permeate fluxes were significantly effected with F/M ratio much more than mixed liquor suspended solids (MLSS). Average flux was for pore sized cellulose acetate membrane. It was concluded that the jet loop membrane bioreactor has distinctive advantages such as the ability to treat high strength wastewater, low area requirements and easy operation.     

Role of hydrodynamic flow parameters in lipase deactivation in bubble column reactor

The dynamic environment within the bioreactor and in the purification equipment is known to affect the activity and yield of enzyme production. In the present work, the effect of hydrodynamic flow parameters and τ_N,max) and interfacial flow parameters ( and ) on the activity of lipase has been comprehensively investigated in bubble column reactors. Lipase solution was subjected to hydrodynamic flow parameters in 0.15 and 0.385 m i.d. bubble column reactors over a wide range of superficial gas velocity (0.01<V_G<0.4-). The flow parameters were estimated using an in-house CFD simulation code based on k-ε approach. The extent of lipase deactivation in both the columns was found to increase with an increase in hydrodynamic and interfacial flow parameters. However, at equal value of any of these parameters, the extent of deactivation was different in the two columns. The rate of deactivation was found to follow first order kinetics. An attempt has been made to develop rational correlations for the extent of deactivation as well as for the deactivation constant. The rate of deactivation was found to be depending on the average turbulent normal stress and interfacial flow parameters such as bubble diameter and bubble rise velocity.