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.     

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.     

SELECTIVE GAS ABSORPTION UNDER PRESSURE

For selective removal of H2S from much larger quantities of CO₂ under pressure, an industrial prototype spray column has been constructed. Sodium hydroxide solution was atomized by a pressure nozzle of special design and entered the scrubber as fine spray to contact the sour gases.

Several operating variables were examined in order to indicate optimal operating conditions for maximum selectivity of H₂S over CO₂. Fine mist and short contact time favor this selective absorption process. An optimum inlet reactant concentration was found dependent upon the H₂S content relative to CO₂ in the inlet sour gas mixture. A special nozzle/shield configuration to avoid contact of sour gas with highly turbulent liquid during droplet formation significantly improved the selectivity.     

Conceptual model-based design and environmental evaluation of waste solvent technologies: Application to the separation of the mixture acetone-water

In this paper, two waste solvent technologies are presented as alternatives to the disposal of spent acetone-water mixtures.

In the first alternative, a batch rectifier is used to concentrate the waste in order to obtain a distillate with a higher calorific value, which is then sent to off-site incineration either in a cement kiln or in a conventional waste solvent incinerator. The second alternative is a hybrid process composed by a batch rectifier and a pervaporation unit that processes in batchwise mode the first cut from the distillation task to obtain a dehydrated solvent. Here, four scenarios are considered, comprising two kinds of membrane materials and two different vacuum systems.

For each alternative, the conceptual design was carried out with the aid of conceptual models of the unit operations involved. Quasi-optimal values for design and operation variables were used as input data to perform an economical and an environmental assessment of each alternative. The economic analysis suggests that the hybrid process is the best alternative given that the replacement cost of fresh solvent (about 850 U$S/ton) is considered as a credit value.

From the environmental analysis with life cycle assessment, two main conclusions can be drawn: i) the use of the distillate as an alternative fuel in a cement kiln leads to a reduction in emissions that is relevant for the categories related to human health and ecosystem quality; and ii) in terms of resource depletion, the hybrid process distillation/pervaporation with the ceramic membrane HybSi (Pervatech) shows the lowest impact due to the solvent recovery.     

Reactions of ketene dithioacetal for a new versatile synthesis of 4,5-substituted 3-aminothiophene-2-carboxylate derivatives

Poly substituted 3-aminothiophenes were successfully synthesized in good yields by using a one-pot protocol via ketene S,S-acetal as an intermediate in basic medium (K₂CO₃/N,N-dimethylformamide) followed by Dieckmann condensation with ethyl bromoacetate. Further, chemistry of thiophenes was explored using active functional groups such as C₃–NH₂, C₄–CN and C₅–SCH₃ on the thiophene nucleus.

Synthesis of ethyl 3-acetamido-4-cyano-5-(methylthio)thiophene-2-carboxylate derivatives and ethyl 3-amino-4-carbamoyl-5-(methylthio)thiophene-2-carboxylate derivatives.     

A RELATIONSHIP BETWEEN CHEMICAL STRUCTURE AND THE CRITICAL TEMPERATURE

Six distillation column models have been used in studies of the usefulness of the Inverse Nyquist Array (INA) method for design of dual composition control for distillation. Five of the column models are experimental, one describing an industrial column, the others four pilot plants. One column model is obtained by modeling from first principles.

The control strategies investigated and compared are multiloop SISO, 2-way decoupling and l-way decoupling. The control variables are the standard ones, i.e. reflux flow and boilup.

In most of the cases INA has been found to be a useful tool for design of the loops and for comparison of the different control approaches. INA has also been found to be useful for simultaneous tuning of the decouplers and the feedback controllers.

For 2-way decoupling the criterion to minimize interaction at the critical frequency for each primary feedback loop has been found useful in most, but not all, cases. The scheme can be designed by pure gains in the decouplers and there is no reason to introduce dynamics into the decouplers—the systems studied are already sufficiently rich in dynamics.

INA has been found to be a suitable vehicle for the choice between the two possible l-way decoupling schemes.

With the design approach taken, l-way decoupling has been found to provide considerably better control quality than 2-way decoupling in two of the six systems, the differences in control quality being small in the other cases.

The effect of model mismatching on the results, caused e.g. by process nonlinearities, is discussed and simple rules to decrease the parameter sensitivity for 2-way decoupling schemes are given. When model mismatching is considered, the advantage of l-way decoupling over 2-way decoupling seems to increase.

One deficiency of the INA design as used in this paper is that it does not single out the design which is to be preferred on the grounds of robustness.     

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.     

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     

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.     

“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     

RADIAL FLOW HOLLOW FIBERREVERSE OSMOSIS: EXPERIMENTS AND THEORY

The performance of a hollow fiber reverse osmosis system is studied both theoretically and experimentally. Experiments were carried out for applied pressure ranging from 200 to 400 psig, feed rates varying from 75 to 380 cc/sec and for feed concentrations up to 34,000 ppm of sodium chloride.

A mathematical model is proposed to predict productivity, ?, and product concentration, θ_p. The model involves solving membrane transport equations simultaneously with the hydrodynamic equations. The solubility-diffusion-imperfection, or pore diffusion model, is used to describe solute and solvent transport across the membrane. The axial gradients of shell side concentration, neglected in previous investigations, are taken into account. The differential equations are solved numerically by the 4th Order Runge-Kutta method.

Predicted values of ? and θ_p agree within 8% and 17% respectively, with experimental data over the entire range of operating conditions. However, membrane transport coefficients were found to be concentration dependent.

An approximate analysis shows that the concentration polarization is negligible in present day hollow fiber systems.     

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.     

Controlling Blown Polyethylene Film Optical Properties

The conventional blown process imparts an inherent haze to the product. The percentage of haze varies with certain process variables:

1. Surface irregularities caused by melt flow phenomena

2. Crystallization behavior

3. Melt drawing phenomena in certain types of polyethylene     

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.     

Recent Advances in Flame Retardancy of Polymeric Materials (Materials,Applications, Industry Developments,Markets)

The Fifth Annual Conference on Flame Retardancy was held May 24–26, 1994, at the Ramada Plaza Hotel, Stamford, Connecticut, USA. The conference was organized by Business Communications Company, Inc., Norwalk, Connecticut (Company President, Mr. Louis Naturman; Conference Coordinator, Mrs. Sharon D. Faust). New materials (polymers, blends, composites), their applications, industry developments, and markets were considered. Specifically, the most important topics were:

Introduction of new technological achievements and development in the field of flame retardancy (FR)

Review of the current state of science and technology in FR

Review of applications and markets for FR products

Presentation of recent developments in local and global standardization and in testing technology

Discussion of toxicity and environmental issues

Provision of a unique opportunity for newcomers to FR research technology and marketing to become acquainted with the FR field in all its aspects

Discussion of halogen-based and non-halogen-based flame retardant chemicals, syngergism, intumescence, FR mechanisms, modeling, flame parameters, inherently FR polymers, and polymer blends     

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.     

Simulations of Promising Indolizidine—α6-β2 Nicotinic Acetylcholine Receptor Complexes

Smoking-cessation drugs bind many off-target nicotinic acetylcholine receptors (nAChRs) and cause severe side effects if they are based on nicotine. New drugs that bind only those receptors, such as α6β2* nAChR, implicated in nicotine addiction would avoid the off-target binding. Indolizidine (-)-237D (IND (-)-237D), a bicyclic alkaloid, has been shown to block α6β2* containing nAChRs and functionally inhibit the nicotine-evoked dopamine release. To improve the affinity of indolizidine (-)-237D for α6β2*, we built a library of 2226 analogs. We screened virtually the library against a homology model of α6β2 nAChR that we derived from the recent crystal structure of α4β2 nAChR. We also screened the crystal structure of α4β2 nAChR as a control on specificity. We ranked the compounds based on their predicted free energy of binding. We selected the top eight compounds bound in their best pose and subjected the complexes to 100 ns molecular dynamics simulations to assess the stability of the complexes. All eight analogs formed stable complexes for the duration of the simulations. The results from this work highlight nine distinct analogs of IND (-)-237D with high affinity towards α6β2* nAChR. These leads can be synthesized and tested in in vitro and in vivo studies as lead candidates for drugs to treat nicotine addiction.