A three‐phase fluidized bed reactor in the combined anaerobic/aerobic treatment of wastewater

Aerobic degradation or polishing is an essential step in the combined anaerobic/aerobic treatment of wastewater. In this study, a type of porous glass beads was used for immobilization of microbial cells in a three‐phase aerobic fluidized bed reactor (AFBR) with an external liquid circulation. The effects of superficial gas and liquid velocities on bed expansion, solid and gas hold‐ups and specific oxygen mass transfer rate, k_La, were investigated. A tracer study showed that the mixing and flow pattern in the 8 dm³ reactor could be simulated by a non‐ideal model of two continuous stirred tank reactors (CSTRs) in series. By treating an effluent from an upflow anaerobic sludge blanket (UASB) digester, the distribution of suspended and immobilized biomass in the reactor as well as the kinetics of COD removal were determined. The specific oxygen mass transfer rate, k_La, at a superficial gas velocity of 0.7 cm s⁻¹ dropped by about 30% from 32 h⁻¹ in tap water to 22 h⁻¹ after a carrier load of 15% (v/v) was added. The measured k_La further dropped by about 20% to 18 h⁻¹ in the wastewater, a typical value of the bubbling fermenters with no stirring. Compared with the aerobic heterotrophs under optimum growth conditions, the microbes in this reactor which was fed with anaerobic effluent plus biomass behaved like oligotrophs and showed slow specific COD removal rates. This might be attributed to the presence of a significant amount of obligate anaerobes and facultative organisms in the aerobic reactor. This was confirmed by a relatively low intrinsic oxygen uptake rate of the microbial population in the reactor, 94 mg O₂ dm⁻³ h⁻¹ or 19 mg O₂g VS⁻¹ h⁻¹. © 1999 Society of Chemical Industry     

Modelling of Cr(VI) removal from polluted groundwaters by ion exchange

This work reports the viability and modelling of the removal of Cr(VI) from polluted groundwaters by means of ion exchange using the resin Lewatit MP‐64. Feed groundwaters that contained Cr(VI) at an average concentration of 2431 mg dm^?3 and 1187 mg dm^?3 of chloride and 1735 mg dm^?3 of sulfate as main anions were acidified to a pH of 2.0 prior to the removal process. Dynamic experiments were carried out in a fixed bed column with feed waters at flow rates in the range of 2.78 × 10^?7 m³ s^?1 to 5.55 × 10^?7 m³ s^?1. Regeneration was achieved with NaOH (2 mol dm^?3). From the experimental results, the equilibrium of the ion exchange reaction was successfully modelled, obtaining an equilibrium constant (K′_AB) = 44.90. Finally, a mass balance that included mass transfer resistances in the liquid and solid phases was developed and from the comparison between simulated and experimental data the value of the effective intraparticle diffusivity (D_s) was determined as 1.43 × 10^?12 m² s^?1. Copyright © 2004 Society of Chemical Industry     

Equilibrium and kinetic studies on the extraction of gadolinium(III) from nitrate medium by di‐2‐ethylhexylphosphoric acid in kerosene using a single drop technique

The liquid–liquid extraction of Gd(III) from aqueous nitrate medium was studied using di‐2‐ethylhexylphosphoric acid (HDEHP) in kerosene. On the basis of the slope analysis data, the composition of the extracted species was found to be [Gd A₃(HA)] with the extraction equilibrium constant (K_ex) = (1.48 ± 0.042) × 10^?12 mol dm^?3. The results of the effect of temperature on the value of the equilibrium extraction constant indicated the endothermic character of the extraction system. The kinetics of the forward extraction of Gd³⁺ from nitrate medium by HDEHP in kerosene was investigated using the single drop column technique. The rate of flux (mass transfer per unit area) was found to be proportional to [Gd(III)], [H₂A₂]_(o), [NO₃^?], and [H⁺]^?1 in the liquid drop organic phase. The forward extraction rate constant, k_f, was 2.24 × 10^?3 m s^?1 using the equation: Copyright © 2005 Society of Chemical Industry     

Anaerobic and aerobic treatment of a simulated textile effluent

A simulated textile effluent (STE) was generated for use in laboratory biotreatment studies; this effluent contained one reactive azo dye, PROCION Red H‐E7B (1.5 g dm⁻³); sizing agent, Tissalys 150 (1.9 g dm⁻³); sodium chloride (1.5 g dm⁻³) and acetic acid (0.53 g dm⁻³) together with nutrients and trace elements, giving a mean COD of 3480 mg dm⁻³. An inclined tubular anaerobic digester (ITD) was operated for 9 months on the STE and a UASB reactor for 3 months. For a 57 day period anaerobic effluent from two reactors, a UASB and an ITD, was mixed and treated in an aerobic stage. In days 77–247 68% of the true colour of PROCION Red H‐E7B was removed by anaerobic treatment with no colour removal aerobically and up to 37% COD was removed anaerobically, with a corresponding BOD removal of 71%. For combined anaerobic and aerobic treatment a mean COD removal of 57% and BOD removal of 86% was achieved. Operation of the ITD at a 2.8 day HRT (volumetric loading rate (B _v) 1.24 g COD dm⁻³day⁻¹) and the UASB at a 2 day HRT (B _v 1.74 g COD dm⁻³day⁻¹) gave comparable COD removals but the UASB gave better true colour removal. Effluent from the combined process operating on this simulated waste still contained an average 1500 mg COD dm⁻³, and further treatment would be required to meet consent standards. © 1999 Society of Chemical Industry     

Improved Synthesis and X‐Ray Structure of 5‐Aminotetrazolium Nitrate

5‐Aminotetrazolium nitrate was synthesized in high yield and characterized using Raman and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁵N). The molecular structure of 5‐aminotetrazolium nitrate in the crystalline state was determined by X‐ray crystallography: monoclinic, P 2₁/c, a=1.05493(8) nm, b=0.34556(4) nm, c=1.4606(1) nm, β=90.548(9)°, V=0.53244(8) nm³, Z=4, ϱ=1.847 g cm⁻³, R₁=0.034, wR₂ (all data)=0.090. The thermal stability of 5‐aminotetrazolium nitrate was determined using differential scanning calorimetry; the compound decomposes at 167 °C. The enthalpy of combustion (Δ_combH) of 5‐aminotetrazolium nitrate ([CH₄N₅]⁺[NO₃]⁻) was determined experimentally using oxygen bomb calorimetry: Δ_combH([CH₄N₅]⁺[NO₃]⁻)=−6020±200 kJ kg⁻¹. The standard enthalpy of formation (Δ_fH°) of [CH₄N₅]⁺[NO₃]⁻ was obtained on the basis of quantum chemical computations at the electron‐correlated ab initio MP2 (second order Møller‐Plesset perturbation theory) level of theory using a correlation consistent double‐zeta basis set (cc‐pVTZ): Δ_fH°([CH₄N₅]⁺[NO₃]⁻(s))=+87 kJ mol⁻¹=+586 kJ kg⁻¹. The detonation velocity (D) and the detonation pressure (P) of 5‐aminotetrazolium nitrate were calculated using the empirical equations by Kamlet and Jacobs: D([CH₄N₅]⁺[NO₃]⁻)=8.90 mm μs⁻¹ and P([CH₄N₅]⁺[NO₃]⁻)=35.7 GPa.     

Solvent extraction of silver(I) from nitrate media using thiourea derivatives

Liquid–liquid extraction of Ag(I) from nitrate solutions using N‐(N′,N′‐diethyl thiocarbamoyl)‐N″‐phenylbenzamidine (TCBA) and 1‐6,‐diethylcarbamoyl imino‐1,6‐diphenyl‐2,5 dithiahexane (TCTH) dissolved in cumene has been studied. The extraction of Ag(I) from 1 mol dm⁻³ NO₃⁻ solutions by TCTH and TCBA was investigated as a function of several variables: equilibration time, organic phase diluent, pH of aqueous phase, Ag(I) and NO₃⁻ concentration in aqueous phase as well as TCBA and TCTH concentrations. Experimental equilibrium data were analysed numerically using the programs LETAGROP‐DISTR and LETAPL and the results showed that Ag(I) extraction could be explained assuming the formation of AgL and AgNO₃HL with TCBA (HL) and AgNO₃S with TCTH (S). The metal extraction was not influenced significantly by the structures of the thiourea derivatives used as extractants. The back extraction of Ag(I) from loaded organic phase was performed using different strippants and 0.5 mol dm⁻³ NaSCN was found to be efficient for this purpose. © 2000 Society of Chemical Industry     

Hydrodynamics,Mass Transfer and Gas Scrubbing in a Co‐current Droplet Column Operating at High Gas Velocities

The main objective of this work was to propose a new process for household fume incineration treatment: the droplet column. A feature of this upward gas‐liquid reactor which makes it original, is to use high superficial gas velocities (13 m s^–1) which allow acid gas scrubbing at low energy costs. Tests were conducted to characterize the hydrodynamics, mass transfer performances, and acid gas scrubbing under various conditions of superficial gas velocity (from 10.0 to 12.0 m s^–1) and superficial liquid velocity (from 9.4·10^–3 to 18.9·10^–3 m s^–1). The following parameters characterized the hydrodynamics: pressure drops, liquid hold‐ups, and liquid residence time distribution were identified and investigated with respect to flow conditions. To characterize mass transfer in the droplet column, three parameters were determined: the gas‐liquid interfacial area (a), the liquid‐phase volumetric mass transfer coefficient (k_La) and the gas‐phase volumetric mass transfer coefficient (k_Ga). Gas absorption with chemical reaction methods were applied to evaluate a and k_Ga, while a physical absorption method was used to estimate k_La. The influence of the gas and liquid velocities on a, k_La, and k_Ga were investigated. Furthermore, tests were conducted to examine the utility of the droplet column for the acid gas scrubbing, of gases like hydrogen chloride (HCl) and sulfur dioxide (SO₂). This is a process of high efficiency and the amount of pollutants in the cleaned air is always much lower than the regulatory European standards imposed on household waste incinerators.     

The Synthesis and Energetic Properties of 5,7‐Dinitrobenzo‐1,2,3,4‐tetrazine‐1,3‐dioxide (DNBTDO)

Energetic tetrazine‐1,3‐dioxide, 5,7‐dinitrobenzo‐1,2,3,4‐tetrazine‐1,3‐dioxide ( DNBTDO ), was synthesized in 45 % yield. DNBTDO was characterized as an energetic material in terms of performance (V_det 8411 m s⁻¹; p_{C J} 3.3×10¹⁰ Pa at a density of 1.868 g cm⁻³), mechanical sensitivity (impact and friction as a function of grain size), and thermal stability (T_dec 204 °C). DNBTDO exhibits a sensitivity slightly higher than that of RDX , and a performance slightly lower (96 % of RDX ).     

Biocatalysis of Chlorophyllase in Ternary Micellar Systems Using Pheophytins as Substrates

The partially purified chlorophyllase, obtained from the alga Phaeodactylum tricornutum, was assayed for its hydrolytic activity towards the pheophytin in ternary micellar systems of hexane/Tris–HCl/surfactant. A wide range of surfactants, sorbitans (Span 20, 40, 60, 80 and 85) and polysorbates (Tween 20, 40, 60, 80 and 85), was used. The use of either 50 μmol dm⁻³ of Span 85 or 1 μmol dm⁻³ of Tween 80 increased the hydrolytic activity of chlorophyllase by 110 and 23%, respectively. The optimum values of pH, enzyme content, incubation time and temperature for the hydrolytic activity of chlorophyllase were determined as 8·25, 8·00 μg protein cm⁻³, 60 min and 27·5°C, respectively. The V_max and K_m values were 6·91 nmole hydrolyzed pheophytin mg⁻¹ protein min⁻¹ and 47·2 nmole pheophytin dm⁻³, respectively, in the Span 85 medium and 10·04 and 121·00, respectively, in the Tween 80 medium. The addition of optimized amounts of individual membrane lipids, L -α-phosphatidylcholine, L -α-phosphatidyl-DL -glycerol and β-carotene increased the hydrolytic activity of chlorophyllase by 50, 36 and 10%, respectively, for Span 85 and 30, 48 and 15%, respectively, for Tween 80. Phytol showed a competitive inhibitory effect on chlorophyllase activity in both Span and Tween systems with a K_i value of 15·5 and 14·3 μmol dm⁻³, respectively. High-performance liquid chromatography and spectrophotometry analyses were used to characterize the end-products of chlorophyllase hydrolytic reaction. © 1997 SCI.     

Correlation Between Photoluminescence and Structural Defects in Ca1+xCu3−xTi4O12 Systems

Ca_1+xCu_{3 ? x}Ti₄O₁₂ powders were synthesized by a conventional solid‐state reaction. X‐ray diffraction (XRD) was performed to verify the formation of cubic CaCu₃Ti₄O₁₂ (CCTO) and orthorhombic CaTiO₃ (CTO) phases at long range. Rietveld refinements indicate that excess Ca atoms added to the Ca_{1 ? x}Cu_{3 ? x}Ti₄O₁₂ (x  =  1.0) composition segregated in a CaTiO₃ secondary phase suggesting that solubility limit of Ca atoms in the CaCu₃Ti₄O₁₂ lattice was reached for this system. The FE‐SEM images show that the Ca_1+xCu_{3 ? x}Ti₄O₁₂ (0  <  x  <  3) powders are composed of several agglomerated particles with irregular morphology. X‐ray absorption near‐edge structure spectroscopy (XANES) spectra indicated [TiO₅V_o^z]‐[TiO₆] complex clusters in the CaCu₃Ti₄O₁₂ structure which can be associated with oxygen vacancies (V_o^z  =  V_o^x, V_o^?, and V_o^??) whereas in the CaTiO₃ powder, this analysis indicated [TiO₆]–[TiO₆] complex clusters in the structure. Ultraviolet‐visible (UV–vis) spectra and photoluminescence (PL) measurements for the analyzed systems revealed structural defects such as oxygen vacancies, distortions, and/or strains in CaCu₃Ti₄O₁₂ and CaTiO₃ lattices, respectively.     

Ion Exchange of the Organometallic Aqua‐Ion fac‐[99mTc(CO)3(H2O)3]+ from Aqueous Solutions

Dynamic (column) studies on the ion exchange of triaquatricarbonyltechnetium(I) cation, fac‐[^99mTc(CO)₃(H₂O)₃]⁺ (1), in the system: amphoteric ion exchange resin (Purolite S‐950) ‐ aqueous HNO₃ solutions (0.05–2 M) corroborate the +1 charge of 1. Stability constants of fac‐[^99mTc(CO)₃(H₂O)_3?nCl_n]^1?n complexes, determined from the distribution coefficients in the system anion exchanger (Dowex 1X4) ‐ aqueous HCl solutions (0.1–12 M) differ from the literature values determined at a constant ionic strength. This difference, resulting from the decrease in the activity of water with increasing HCl concentration, may be a measure of the effect of non‐constant ionic strength on ion‐exchange equilibria. Weak acidic properties of 1 in aqueous solution at n.c.a. (no carrier added) level (pK_a ?9) have been demonstrated by paper electrophoresis.     

Compression creep of molten low-density polyethylene

Viscoelastic parameters of low-density polyethylene melt (LDPE) in compression creep have been measured. Volume deformation (k%) increases as pressure (P) increases and temperature (T) decreases. Plots of the bulk creep compliance B(t) vs. time (t) may be shifted to provide master curves. As the pressure and the temperature increase, the pressure shift factors (b_p and a_p) increase almost linearly [activation volumes (ΔV^*) varying from 1.0 to 15.0 cm³ mol], while the temperature-shift factors (b_T and a_T) decrease. The steady-state creep compliance (B^s) describes the recoverable storage of elastic energy (Be) and seems to be related to the extrusion die-swell (B^s_c/B^s_d). Volume viscosity (η_K) decreases with increasing stress (P) and increasing temperature (T).     

The Facile Synthesis and Energetic Properties of an Energetic Furoxan Lacking Traditional “Explosophore” Moieties: (E,E)‐3,4‐bis(oximomethyl)furoxan (DPX1)

Energetic furoxan (E,E)‐3,4‐bis(oximomethyl)furoxan (DPX1) was synthesized in 75 % yield, using a literature procedure, from a precursor readily available in one step from nitromethane. DPX1 was characterized for the first time as an energetic material in terms of calculated performance (V_det = 8245 m s⁻¹; p_C‐J = 29.0 GPa) and measured sensitivity (impact: 10 J; friction: 192 N; T_dec: 168 °C). DPX1 exhibits a sensitivity less than that of RDX, and a performance significantly higher than 2,4,6‐trinitrotoluene (TNT).     

The phase structure,thermodynamic properties,and dissolution behavior of Ca5Mg4V6O24

A Ca₅Mg₄V₆O₂₄ compound was synthesized through solid-state roasting routes under an air atmosphere, and its crystal structure and thermodynamic properties were determined using various methods. The cell parameters of Ca₅Mg₄V₆O₂₄ indicate that it crystallizes in cubic space group Ia3d with the unit cell parameters a = 12.442 ± 0.001 Å. X-ray photoelectron spectroscopy also confirmed that the vanadium element in the Ca₅Mg₄V₆O₂₄ sample is present in the +5 state. The melting of Ca₅Mg₄V₆O₂₄ was detected at 1442 K. The molar heat capacity (374 J mol K⁻¹) and entropy (688.2 J mol K⁻¹) of Ca₅Mg₄V₆O₂₄ at 298.15 K were determined using physical properties measurement system, and simultaneous thermal analyzer for the first time. The solubility of Ca₅Mg₄V₆O₂₄ in water at different temperatures was measured and its dissolution behavior in sulfuric acid and kinetics was experimentally established.     

Graft copolymerization of methacrylic acid onto xanthan gum by Fe2+/H2O2 redox initiator

The graft copolymer of xanthan gum with methacrylic acid was synthesized in inert atmosphere by using Fentos reagent as a redox initiator. The effect of reaction conditions on grafting parameters [G(%), E(%), C(%), A(%), H(%), and R_g] was investigated. Similar trend was observed on increasing the concentration of ferrous ion and hydrogen peroxide from 4.0 to 20.0 × 10^?3 mol dm^?3 and 2.5 to 10 × 10^?3 mol dm^?3 respectively, i.e., initially grafting parameters increased and after a certain range of concentration grafting parameters showed decreasing trend. Hydrogen ion shows influenced result i.e., small increment of concentration in hydrogen ion presents much increment in percent of grafting. It was observed that the [G(%), E(%), C(%), A(%), and R_g] increased upto 6.67 × 10^?2 mol dm^?3 concentration of methacylic acid after that it decreased. Maximum G(%) was obtained at minimum concentration of xanthan gum i.e., at 40 × 10^?2 g dm^?3. The optimum temperature and time duration of reaction for maximum percentage of grafting were found to be 45°C and 150 min respectively. Thermogravimetric analysis showed that the xanthan gum‐g‐methacrylic acid is thermally more stable than pure gum. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Gas-liquid mass transfer in “dead-end” autoclave reactors

Gas-liquid volumetric mass transfer coefficients, (k_La), have been obtained for “dead-end” autoclave reactors operated in two different modes: (a) gas introduced into the gas phase, and (b) gas introduced through a dip-tube in the liquid. Three different methods of k_La determination have been compared. Effects of agitation speed, impeller diameter, gas to liquid volume ratio (V_g/V_L), position of the impeller and reactor size on k_La have been investigated. The k_La data were found to be correlated as: k_La = 1.48 × 10^?3 (N)^2.18 (V_g/V_L)^1.88 (d_I/d_T)^2.16 (h₁/h₂)^1.16 The critical speed of surface breakage, at which transition from the surface convection to the surface entrainment regime occurs, was also determined for different impeller positions, impeller diameters and gas to liquid volume ratios.     

Calcium and fluoride release from ion exchange polyphasic systems

The present study concerns the kinetics of ion exchange accompanied by CaF₂ precipitation in tri‐phasic and quadri‐phasic systems involving a weak base anionic exchanger and a carboxylic cationic exchanger in the F^? and Ca²⁺ forms, respectively, in contact with a solution of artificial saliva. It was shown that in both systems the rate of Ca²⁺ release from the cationic exchanger is much lower than that of F^? from the anionic one. The rate of release for both ions, controlled by intraparticle diffusion, has been characterized by a Fick's law model. The kinetic parameters of effective rate of release (B) and diffusion coefficient (D) of the respective ion in the resin phase depend on the type of resin and the presence of different numbers of phases. The amount of the precipitate crystallizing on the surface of the resin beads depends on the type of the ion exchange resin, its particle size and on the ratio of resin components. By varying this ratio and the particle size of the ion exchangers it is possible to accomplish the precipitation mostly on the larger surface of the ionic exchanger. Copyright © 2003 Society of Chemical Industry     

A contribution to the measurement of oxygen mass transfer in a laboratory pressure reactor

A method was used to measure the liquid‐side volumetric coefficient of oxygen mass transfer (k_La) in closed, semi‐batch pressure reactors used in hydrometallurgical laboratories. In this method, the oxygen pressure was monitored as oxygen was continuously sparged into a pressure vessel containing a sodium sulfite solution. A material balance equation was derived for oxygen in the vessel and the experimental data were fitted to this equation. From the constant parameters of the equation, k_La was calculated. The solution in the vessel also contained an appropriate amount of cobalt catalyst so that oxygen was consumed rapidly by oxidation of sulfite to sulfate. Under these conditions, the oxygen concentration in the bulk liquid phase could be assumed to be equal to zero. Values of k_La determined by the method under various conditions were reproduced within 12% deviation from the average values. k_La was found to increase moderately with temperature in the range of 25 to 75 °C, with an activation energy of 33.09 ± 1.33 kJ mol⁻¹. The presence of hydrophobic or hydrophilic solids was found to have a deleterious effect on k_La. © 2000 Society of Chemical Industry     

An electrochemical hydrocyclone cell for the treatment of dilute solutions: approximate plug-flow model for electrodeposition kinetics

The mass transfer conditions in a hydrocyclone cell have been analysed and an approximate plug-flow model has been developed to describe metal ion depletion during batch recycle operation. The resulting concentration-time relationship and reaction rate equation has been shown to describe satisfactorily the experimental data obtained for the electrodeposition of copper and silver from dilute solutions. Moreover, these relationships have enabled the evaluation of mass transfer coefficients in the hydrocyclone cell.List of symbols a ₁,a ₂,b numerical exponents - C concentration (mol dm^–3) - C _o initial bath concentration (mol dm^–3) - C(0) cell inlet concentration (mol dm^–3) - C(L) cell outlet concentration (mol dm^–3) - k rate constant (h^–1) - K mass transfer coefficient (ms^–1) - K _L volumetric mass transfer coefficient = 2RLK (m³ s^–1) - L active length of the cylindrical cathode (m) - Q volumetric flow rate (m³ s^–1) - r inside radius of the conical part of the cell - r _A reaction rate of component A (mol dm^–3 h^–1) - R inside radius of the cylindrical part of the cell (m) - t time - u vertical (axial) velocity in the annulus - U cell voltage (V) - _t horizontal (tangential) velocity in the annulus - V _B volume of the reservoir/bath - V _R volume of the cell/reactor - _B residence of time of the reservoir     

Selection and isolation of glucose-tolerant amylolytic Aspergillus by cyclic fed batch culture process

A simple cyclic fed batch culture system was developed for selection and subsequent isolation of glucose-tolerant Aspergillus niger strain. A culture medium which contained 1.2 g dm⁻³ of glucose was inoculated with a non-glucose-tolerant A. niger (K_i =20.25 g dm⁻³). A culture medium of higher glucose concentration (100 g dm⁻³ and 200 g dm⁻³) was fed at a rate equal to the rate of HN₄⁺ consumption by means of a pH control system. The maximum and minimum liquid levels in the fed batch culture vessel were determined by two liquid level detectors which activated and deactivated a harvest pump. The novelty of the selection system is that the frequency and pressure of selection increase gradually but continuously, and they are determined by the intrinsic potential of the culture. The process was fully automatic. An Aspergillus mutant which had a glucose inhibition constant of 3200 g dm⁻³ was isolated after six generations. The process should be particularly useful for screening filamentous microorganisms growing on novel substrates or tolerating inhibitors.