IN SITU LEACHING OF URANIUM USING DILUTE SULFURIC ACID AND MOLECULAR OXYGEN

The technical feasibility of in situ uranium leaching using dilute sulfuric acid and molecular oxygen has been assessed and the important process parameters examined by use of laboratory high pressure leaching columns.

The dilute H₂SO₄/O₂ lixiviant was effective in leaching uranium from the ore samples tested. The leaching process was chemical reaction rate limited and can be represented using pseudo first-order kinetics. The leaching rate constant is proportional to the proton concentration of the lixiviant.

Much of the uranium was leached from the ore before decomposition of carbonate minerals by the acid was complete. Acid consumption per pound of U₃O₈ increased sharply as the uranium recovery level exceeded 70%. There appears to be a minimum oxygen pressure for effective uranium leaching. A pressure of 2758 KPa was adequate for the ore samples tested     

Hydroxyl Radical Oxidation Processes For The Removal Of Triazine From Natural Water

The purpose of this study was to point out processes that can provide triazine oxidation via hydroxyl radical production in a water treatment line. We focus our attention on:

- oxido-flocculation, using Fe²⁺, H₂O₂

- inter-oxidation, using O₃, H₂O₂ and eventually an heterogeneous catalyst.

- disinfection, using UV, O₃ and H₂O₂ combinations.

Results show that triazines can be removed by all these processes with different efficiencies. At full scale, the O₃/H₂O₂ process presents the best performances from an economical and technical point of view.     

“SPURT FRACTURE” IN CAPILLARY FLOW

The critical conditions under which flow curves in capillary flow abruptly change their slope to zero (spurt) and the influence of solvent additive and solvent power on this phenomenon have been investigated. Based on a forced high elastic state concept an expression for the so-called spurt phenomenon, i.e. fracture-induced slip at the wall in a capillary of a capillary rheometer, is deduced. It is found that the spurt fracture stress, τ^s _cr, and the spurt fracture shear rate, γ^s _cr, can be represented by the master curve log (τ ^s _crr ((p/M_c)PE(M_c/p))^2/3 against log (a_T γ^s _cr), where a_T is the WLF shift factor, M_c the molecular weight between entanglements and p the density.

Estimation of slip rates at the wall and measurements on slightly crosslinked high density polyethylene supports the assumption that spurt results from melt fracture at the capillary wall.

Only addition of the non-solvent calcium stearate (with high density polyethylene) results in flow behavior which significantly deviates from that found for samples containing good solvents. Gel permeation chromato-graphy indicates that if chain scission resulting in lower molecular weight takes place, it will be limited to thin layers near the capillary wall.

melt fracture in the capillary cannot be reached. The flow behavior is influenced by addition of the non-solvent calcium stearate. The slopes of the flow curves is changed at relatively low shear rates but the high molecular weight polymer DMDS 5140 never the less shows spurt behavior at the same stress as for the pure sample.

This behavior may tentatively be interpreted as being caused by the formation of a boundary layer of non-solvent at low shear rate the thickness of which depends on the polymer and flow field. At stresses corresponding to the critical conditions, fracture in the polymer takes place. The interface between the non-solvent layer and the polymer matrix must according to Han61 be expected to be unstable     

UV-induced Decomposition of Ozone and Hydrogen Peroxide in the Aqueous Phase at pH 2–7

The photolysis of ozone and formation of hydrogen peroxide were investigated in solution of pH 2–7, in a 200 cm³ photoreactor in the incident photon flow range 9.6 x 10^?8 - 4.2 x 10^?7 einstein s^?1. The quantum yield of the primary photochemical reactions was measured in a direct way by suppressing the secondary radical reactions. The determined quantum yields of the photo-decompositions of ozone and hydrogen peroxide were 0.42 ± 0.042 ± 0.04 and 0.49 ± 0.04, respectively.

A correct mathematical treatment is given for calculation of the light absorption of the individual components of a multi-absorbent reaction mixture.

On the basis of the literature data and die present results, a probable chemical and reaction kinetic model was proposed to characterize the investigated reaction systems. Reaction kinetic simulations demonstrated that the model predicts a good fit to the measured data with the preferred literature rate constants, except that for the HO₃ radical decomposition reaction. A reasonable reduction of this rate coefficient value is in accordance with the latest published results.     

Extraction and Characterization of Starch from Oak Acorn,Sorghum, and Potato and Adsorption Application for Removal of Maxilon Red GRL from Wastewater

Pure starch has been isolated from different samples: oak acorn, sorghum, and potato using alkali steep and wet-milling procedure. The structure of the extracted starches was analyzed using Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction. Their physicochemical properties (water content, ash content, pH, amylose content, swelling power, and water solubility index) were determined. The FT-IR spectra of isolated native starches have shown the main bands characterizing the starch. For sorghum starch (SS) and oak acorn starch (OAS), X-ray diffractograms exhibited an A-type diffraction pattern, while potato starch (PS) displayed typical B-type pattern. Compared to sorghum and oak acorn, potato starch has shown the highest level of both swelling power and water solubility index.

To estimate the color removal quality of the extracted starches, a sorption of a dye named maxilon red GRL has been carried onto them.

The results of equilibrium isotherms in batch adsorption process were analyzed according to the Langmuir and Freundlich model. The characteristic parameters were determined for each model. Furthermore, the effect of initial pH and ionic strength on adsorption capacity was considered, and regeneration studies were carried out.     

Comparative study: Correlating extraction efficiency for Hg(II), Cd(II), and Pb(II) metal ions with the chelate stability and total hardness in simple nitrogen donors

Four N-donors (PHDA, ATPH, APHO, and MTAN) containing NH₂ were used to extract Hg(II), Cd(II), and Pb(II). Their extraction capacity was determined by measurement of percentage extraction.

The chelates extract these metals differently: for example, efficiency of ATPH was the highest for Hg(II) compared to PHDA, APHO, and MTAN.

The extraction efficiency was found to depend on: donor atom hardness, chelate total hardness, metal: chelate mole ratio and substituent’s electronic effects. Among all, total hardness and chelate stability are key factors and molecule of small (E_HOMO – E_LUMO) is more reactive, where extraction efficiency increases as molecular stability decreases.     

EFFECT OF CONTAMINANTS ON CRITICAL HEAT FLUX AT LOW PRESSURES

Critical heat flux (CHF) tests were performed to evaluate the effect of dissolved, nonreactive contaminants on low-pressure industrial boilers. These tests were conducted on a 2.38-inch (60.5 mm) I.D. vertical smooth bore tube with nonuniform circumferential heating at pressures between 100 and 500 psia (0.69 and 3.45 MPa). Tests were performed under two water chemistry conditions: clean (less than 1.6 ppm total dissolved solids) and contaminated (greater than 2000 ppm TDS). With all other operating parameters held constant, the following effects of contamination on the steam quality (X) at CHF were determined at the pressures indicated:

At 100 psia (0.69 MPa) X_clean < X_cont

At 300 psia (2.1 MPa) X_clean?X_cont

At 500 psia (3.5 MPa) X_clean > X_cont

The effect of contamination on CHF was found to be a function of pressure, initial contaminant concentration, and the relative steam quality at which CHF conditions occur. These results are compared to data available in the open literature where X_clean is always greater than X_cont. A method for correlating these data is also illustrated.     

Comparison of Ozone and Hydroxyl Radical-Induced Oxidation of Chlorinated Hydrocarbons in Water

The efficiency of ozonation and advanced oxidation processes such as ozone/UV, ozone/H₂O₂ and H₂O₂/UV was assessed for chlorinated hydrocarbons using a closed batch-type system. 1,1-Dichloropropene (DCPE), trichloroethylene (TCE), 1-chloropentane (CPA), and 1,2-dichloroethane (DCA) were used as model compounds.

The direct reaction between substrates and ozone predominated at lower pH, which resulted in the efficient oxidation of the olefin, DCPE. At higher pH, ozonation resulted in more efficient oxidation of the chlorinated alkanes, with a corresponding decrease in the efficiency of DCPE oxidation. Consistent results were observed for ozone/H₂O₂ and ozone/UV treatment. Due to slow UV-induced decomposition of H₂O₂, the process using H₂O₂/UV (254 nm) resulted in very slow oxidation of all four compounds.

The total ozone requirement to achieve a given degree of elimination (to 37% of the original concentration), δ0.37, was used to assess the combined effects of the direct and indirect reactions for different types of waters.     

Iron and Manganese Removal with Ozonation in the Presence of Humic Substances

The conditions for the removal of iron and manganese contained in slightly mineralized water, rich in humic substances, were determined in a case where an intermediate oxidation was provided in a conventional potabilization line comprising a coagulationflocculation stage with iron salts.

The experiments were conducted both on a synthetic water, with or without addition of humic substances, and on raw water from the Moulin-Papon dam. While iron was easily removed by simply increasing the pH measurement from 8.2 to 8.5 without intermediate oxidation, ozonation applied to water with a pH of nearly 8.4 did not enable the manganese to be removed with a low ozone dose (about 1 mg/L) unless a significant amount of bicarbonates (120 to 130 mg/L as CaCO₃) were injected prior to the ozonation-filtration stage.

As it removes the manganese from the water, intermediate ozonation also removes the abatement of organics on the filters, and lowers the THM buildup potential.     

HEAT TRANSFER IN PACKED BED REACTORS WITH ONE PHASE FLOW

An extensive array of literature data on the heat transfer from a reactor wall to a fluid flowing through a packed bed and those obtained from some experimental runs were interpreted with a model containing two parameters: k_e, (effective radial thermal conductivity within the bed) and h_w (heat transfer coefficient at the wall).

Both parameters were considered in terms of a stagnant contribution (due to the heat conduction through the solid particles and the fluid in the void space) and a radial mixing contribution (due to the heat convection by turbulent mechanism.

The stagnant contribution was interpreted with a model similar to that proposed by Kunii and Smith (1966) for heat transfer in a packed bed with motionless fluid.

General correlating equations for calculating the stagnant and the turbulent contributions of both k_e, and h_w are proposed.     

Determination of Residual Ozone or Chlorine Dioxide in Water with ACVK – an Updated Version

The determination of residual ozone or residual chlorine dioxide can be carried out with Acid Chrome Violet K (C.I. code no. 61710, formerly 6170), now available as dye for analytical use under the name of Alizarin Violet 3R (Aldrich 22, 783-8; MW 622.25). The discoloration of the dye in an NH₃-NH₄CI buffered solution of pH 8.1 to 8.5 is specific both for ozone and for chlorine dioxide without interference of chlorine, chloramines, chlorite or chlorate ions in concentrations possibly encountered in treated drinking water.

Detection limit : 0.02 mg L^?l: standard deviation : 0.01 mg L^?l are obtained both for ozone and chlorine dioxide.     

Effect of different application techniques on microshear bond strength of self-etch adhesives to dentin

Objectives: To investigate the effect of different self-etch adhesive systems application techniques: active or passive in a single or double layer on adhesive–dentin microshear bond strength.

Methods: Occlusal surfaces of 48 extracted human molars were ground to expose flat superficial dentin surfaces. Specimens were randomly divided into two main groups according to the tested self-etch adhesive system either: One-step self-etch (Adper^TM easy-one) or two-step self-etch (Adper^TM SE Plus). Each adhesive system was applied on the prepared dentin surfaces followed one of these techniques: (1) Passive application of a single layer, (2) Active application of single layer, (3) Passive application of double adhesive layer (with light curing in between), and (4) Active application of double adhesive layers. Resin composite was packed inside micro-tubes fixed on the bonded dentin surfaces and light cured for 40 s. All specimens were stored in artificial saliva either for 24 h or 3 months before testing. Microshear bond strength test was employed using a universal testing machine at a crosshead speed of 0.5 mm/min.

Results: Adper^TM SE Plus showed higher significant microshear bond strength in compared with Adper^TM easy-one. For both adhesive systems active application showed higher significant microshear bond strength to dentin than passive application. Double application of adhesive systems showed lower microshear bond strength than single application.

Conclusion: Active application of self-etch adhesives could improve the dentin microshear bond strength. Double application with curing in between the layers did not improve the bond strength to the tested adhesive.     

CHLORINATION KINETICS OF Nb2O5

The reaction of single sintered pellets of α-Nb₂O₅ with chlorine and carbon monoxide was studied in the temperature range from 773 K to 1073 K using a thermogravimetric apparatus. The rate controlling step of the reaction was determined from experiments carried out at variable gas flow rates, gas composition, surface geometry, pellet porosity and temperature. The vapor phase transport reaction can be written as:

Nb₂O₅(s) + 3Cl₂ (g) + 3CO(g) = 2NbOCl₃ (g) + 3CO₂(g).

Up to 60% conversion, the amount of volatilized product was found to be directly proportional to the time of reaction. The external surface area of the pellets remains unchanged up to this stage while the intergranular morphology changes.

These results were compared with reaction rates of commercial pyrochlore concentrate in order to establish the fundamental reaction stages of the process of extraction of Nb₂O₅ from pyrochlore.     

Economics of Treating Waste Gases from an Air Stripping Tower Using Photochemically Generated Ozone

Air stripping towers have been recommended for the removal of volatile organic compounds (VOCs) in drinking water supply and industrial waste treatment systems. This technique removes VOCs economically in the liquid phase. It can, however, create adverse secondary environmental impacts by removing VOCs from the water and discharging them to the air.

A commonly proposed method for controlling .VOC emissions is filtration of the off-gas through adsorption of the stripped organics in the off-gas by granular activated carbon. The high incremental cost of this alternative has produced an interest in alternative control technologies.

One alternative currently available is based on short wavelength ultraviolet (UV) radiation. This technique combines the effects of ozone generation, free radical formation and photolysis of the contaminants to effectively control the VOC emissions. This technique is known as Advanced Photo Oxidation (APO)^R.

The cost for APO is $0.27/m³ for a 3.8 m³/hr contaminated water system. A system of this size is adequate for a groundwater decontamination project where a moderate length of time is available for restoration of the site. The cost of a conventional air stripping tower with Granular Activated Carbon (GAC) adsorption emissions control in this size range would be $0.40 to $0.45/m³ (J.M. Montgomery, 1986).

Additional testing will be required to fully develop design guidelines for different contaminants and larger systems. Another area for additional technical documentation is the application of this technique to the liquid phase oxidation of VOCs.     

HEAT TRANSFER IN TRICKLE-BED REACTORS

The mechanism of radial heat transfer in two-phase flow through packed beds is examined. A model with 2 parameters: an effective radial thermal conductivity in the bed, k_e , and a heat transfer coefficient, h_w , at the wall, give a satisfactory interpretation of the radial temperature profile.

k_e was expressed in terms of a stagnant contribution, due to the heat conduction through the solid and the fluid in the void space, and a radial mixing contribution of the gas and liquid phases, due to the radial component of the velocity of both fluids. The radial mixing contribution of the liquid ( k_e ) _L was compared with radial mass dispersion data, and a satisfactory agreement was obtained.

Moreover, ( k_e )was much higher than the gas mixing and the stagnant contributions.

Correlations for hw and k_e ) _L have been proposed in accordance with the hydrodynamic regimes of the two-phase flow.     

Assessment of a Cylindrical and a Rectangular Plate Differential Mobility Analyzer for Size Fractionation of Nanoparticles at High-Aerosol Flow Rates

An existing differential mobility analyzer (DMA) of cylindrical electrodes and a novel DMA of rectangular plate electrodes are demonstrated for size fractionation of nanoparticles at high-aerosol flow rates in this work. The two DMAs are capable of delivering monodisperse size selected nanoparticles (SMPS σ_g < 1.1) at gas flow rates ranging from 200 slm to 500 slm. At an aerosol flow rate of 200 slm, the maximum attainable particle mean size is of about 20 nm for the cylindrical DMA and of nearly 50 nm for the rectangular plate DMA. The number concentration of the monodisperse nanoparticles delivered by the high-flow DMAs spans from 10⁴ cm^?3 to 10⁶ cm^?3 depending upon the particle mean size and particle size dispersion.

Copyright 2014 American Association for Aerosol Research     

Reactivity Studies In The Ozonolysis Of Pollutants Using A Perforated Spinning Disc Reactor To Enhance Mass Transfer

A perforated spinning disc ozone contactor is described with reference to its use as an absorber with simultaneous chemical reaction.

Greatly enhanced mass transfer coefficients k_L are measured whilst simultaneously maintaining low ozone loss. Comparisons of k_L and volumetric coefficient, k_L a values, are made with more conventional packed or bubble columns.

Acetic acid, 2-propanol and 4-nitrophenol, representing a wide reactivity range, are used to elucidate the applicability of rotating contactors in effluent treatment. It has been possible to study the effects of surface activity on mass transfer with subsequent reaction and to generate design data for the next generation of rotating contactors.