APPLICATION OF A SYSTEMATIC APPROACH FOR DETERMINING POSSIBLE REACTION MECHANISMS: METHANOL SYNTHESIS AND ANODIC OXIDATION OF ZINC

A systematic enumeration of possible reaction mechanisms consistent with a given set of chemical species and elementary steps is useful in guiding research in heterogeneous reaction systems which are encountered in catalysis and electrochemistry. In this paper, the synthesis of methanol by catalytic hydrogenation of carbon monoxide and the anoidic oxidation of zinc in alkaline solutions are presented as two examples of the usefulness of such an approach. The technique utilized to generate the reaction mechanisms is based upon combinatorial analysis, linear algebra and the principle of microscopic reversibility.

In the case of methanol synthesis, it is shown that in addition to the two currently proposed mechanisms, there exist two alternate reaction pathways each of which involves the hydrogenation of a formyl species to form a surface methoxide. One of these mechanisms has recently been proposed for a ZnO catalyst, however there remains an additional mechanism for consideration. For the case of anodic zinc oxidation, it is shown that mechanisms which involve cathodic elementary steps are also possible. To the authors knowledge, these mechanisms have not been previously discussed in the literature.     

Removal of Aromatic Nitro Compounds from Water by Ozonation

Experimental studies were carried out on the removal of five species of aromatic nitro hydrocarbons by ozonation. Ultraviolet spectrograms with distinct absorption peaks were plotted for each of them. It has been found that the absorbances of aqueous solutions containing the single compounds mentioned above increase to different extents at the wave lengths ranging from 200 to 230 nanometers with increase of ozone dosages. This is ascribed to the nitrite ions splitting out of the benzene rings and being further oxidized to nitrate ions by ozonation.

It has been indicated that the removal of the five species of aromatic nitro compounds by ozonation can well be expressed mathematically by first order reaction equations. Besides, the reaction constants and half-life periods for various species of the tested nitro compounds were calculated at different temperatures and pH.

An ozonation effect index (OI) was developed in the study to express the degree of degradation of substrates by ozonation, by means of which the five aromatic nitro hydrocarbons were compared with each other and finally ranked in the following order from greatest to smallest degrees of degradation:

p-nitroaniline > nitrobenzene > p-dinitrobenzene > p-nitrotoluene > m-dinitrobenzene

It has also found that the CODm/M ratio increases with ozone doses. This means that some easily degradable intermediates are produced, and increase in concentration with increase of ozone dose in the ozonation process.

The mechanisms of removing the five aromatic nitro hydrocarbons are discussed from the viewpoint of orienting effects of substituent groups on the aromatic rings.     

SIMULATION OF LIGNIN PYROLYSIS

Model compound pyrolysis reaction pathways and kinetics were used in simulation of both native (e.g.. milled wood) and Kraft lignin thermolyses where either only primary or also secondary reactions are important.

Predicted products fell into one of permanent gases, tight liquids, phenolics and carbonaceous residue fractions. Product yields were more dependent on lignin type than on reaction environment.

Comparison of simulation predictions with experimental pyrolyses of actual lignins, accomplished in terms of both product identities and yields, is encouraging. It is noteworthy that the simulations are strictly a priori and incorporate no actual lignin pyrolysis information.     

MEASUREMENT OF INTERFACIAL AREA AND MASS TRANSFER COEFFICIENTS BY CHEMICAL METHOD OF C02 ABSORPTION INTO AQUEOUS SOLUTIONS OF NaOH IN A MODEL COLUMN WITH EXPANDED METAL SHEET PACKING

The theory of gas absorption accompanied by fast pseudo-fast order reaction which considered dependences of diffusivity, kinetic constant and Henry's law constant on absolute temperature and ionic strength was used to obtain values of effective interfacial areas and mass transfer coefficients in gas and liquid phase.

Experimental measurement of carbon dioxide absorption from mixture with air was performed in a pilot-plant column with expanded metal sheet packing irrigated with sodium hydroxide solution.

Resulting liquid and gas-side mass transfer coefficients are compared with values obtained from physical Absorption measurement of carbon dioxide into water and with measurement of gas-side mass transfer coefficient for sulphur dioxide in the same column.

The differences between determined values are discussed.     

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     

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.     

Measurement of the Nanoparticles Distribution in Flat and Pleated Filters During Clogging

It is currently admitted that for each filtration process using pleated filters, at least three steps can be distinguished: depth and surface filtration, which are common to flat filters, and surface reduction. This step is caused by inefficient filling of the pleat due to the filter geometry. For combustion aerosol, it has been proved that this third step strongly depends on the filtration velocity resulting in an increase of the resistance when air flow decreases. This observation leads one to think that Brownian diffusion, higher for low velocities, could influence the clogging dynamic of a pleated filter.

In this article, a protocol derived from the dust cake preparation method published by Schmidt is developed. The aim of this study is to measure the aerosol penetration inside a filter media as well as in a pleat using a scanning electronic microscope and energy dispersive X-ray spectroscopy elementary detection. This method has also been extended to the study of pleated filters to measure the particle distribution inside the pleat. Filters were loaded with nanoparticles in order to evaluate the specificity of the diffusional regime on the clogging of pleated HEPA filters. For pleated filters, two filtration velocities were investigated: 2.5 and 0.2 cm/s.

Copyright 2014 American Association for Aerosol Research     

New Pilot Plant Studies at the Budapest Waterworks

The quality of water provided by the Budapest Waterworks should comply with the standards prescribed by the European Community. According to these provisions, on one of the major water-producing regions (Csepel Island), rows of wells of 60,000 m³/day yield have been closed recently, and in the immediate future further plants would have been closed because of the high iron and manganese content of the water.

The raw water obtained from 100 different wells will be purified by a water treatment plant of 150,000 m³/day capacity. Considering the high iron content (0.05–0.15 mg/L) and manganese content (0.05–0.2 mg/L), the raw water fails to comply with the requirements of the potable water standard.

Since 1990, over a period of three years, we conducted water purification experiments in several stages. In these, three methods of oxidizing as well as single and double layer open rapid filters were applied to oxidize the manganese (and, to a lesser extent, the water) present in dissolved form, resp., to destroy various living organisms.

In the course of the experiments, it became clear that the chlorine and chlorine + air methods are efficient in case of a small quantity of iron to be oxidized and only 20–25% of the dissolved manganese content could be oxidized.

Neither of the two methods could ensure firm management of microbiological and bacteriological characteristics. The best results were obtained by ozone oxidation, in which case the chemical oxidizing process was almost fully completed and even the chlorine-resistant living organisms could be destroyed.

On the basis of the experiments carried out, the investment program of the water treatment plant was worked out and the conditions of an international tender were compiled whose winner will be commissioned to build up the water works in the time period 1993–1996. One of the main steps of the proposed technology is the ozone treatment.     

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.     

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.     

First Year Operation Report of the Corona Discharge Ozone Swimming Pool Water Treatment Systems at the Peck Aquatic Facility,Milwaukee, Wisconsin

The two corona discharge ozone swimming pool water treatment systems installed in the Peck Aquatic Center in Milwaukee, WI now have been in continuous operation since September, 1987. The two pools are part of the Karl Jewish Campus Facility of the Harold and Judy Sampson Campus of the Milwaukee Jewish Community Center.

The operation of these water treatment systems has shown that safe and high quality pool water is obtained reliably and economically. One pool (Main Pool) is of Olympic size, the other (Learner pool) is designed especially for use by children. Both pools utilize a full corona discharge ozone water treatment system. They were the first ozone systems in the U.S. to be built for public pools using the process of ozonation, flocculation, filtration, ozone removal and residual chlorination.

An extensive testing program was initiated in cooperation with the Wisconsin Department of Health. The bacteriological water quality from these swimming pools was in compliance with Wisconsin State Health Regulations and the German DIN Standard 19,643.

The first year of operation of the Peck Aquatic Center has shown that the corona discharge ozone pool water treatment process can:

1) Operate reliably in a public swimming pool environment without the need for highly or special operator qualifications.

2) Produce continuously bacteria- and virus-free pool water without the harmful and unpleasant effects of chlorine.

3) Creates a user constituency group praising and promoting the use of “minimal chlorine swimming” in the community.     

Interactions Between Ozone,Halogens and Organic Compounds

During drinking-water treatment, ozone used as a preoxidant and chlorine required for final disinfection, lead to competing chemical reactions, in the case of raw water containing both organic compounds and inorganic salts (such as bromides and ammonia).

The study of the interactions between those reactants has been made according to the following main topics :

As for THM formation, experiments conducted on simple organic compounds or on natural fulvic acids show important decreases in THM or TCAA formation after ozonation. It may be noticed, however, that the ozonation of surface waters may induce the formation of haloform precursors, usually with a low level of reactivity.

In water supplies containing bromide ions, oxidation of the latter through hypobromous acid may take place during the ozonation stage. Failing preozonation treatment, hypobromous acid is generated very rapidly during chlorination, thus inducing the formation of chloro- brominated organic compounds.

During the ozonation of fulvic acid solutions, the presence of small amounts of bicarbonate was found to improve precursor removal significantly.

It can be concluded that the partial analogy of the action of ozone or chlorine on aromatic structures, whether simple or complex (such as humic and fulvic acids), seems to indicate that the consequence of preozonation is the destruction, at least in part, of the most reactive sites for THM production, thus leading to a decrease of the volatile organochlorinated compounds formed during the post-chlorination. However, some ozonation products of natural waters are THM precursors, though of low reactivity. Then, in the presence of bromide ions, the formation of volatile organobrominated compounds may be observed during ozonation.     

Modeling of nonstationary processes during separation of multicomponent isotope mixtures

The article presents a mathematical model for calculation of nonstationary hydraulic and separation processes in a gas centrifuge (GC) cascade for separation of multicomponent isotope mixtures. The model has been applied to calculate the parameters of nonstationary processes in a GC cascade for separation of krypton, germanium and tungsten isotopes. As a result, the specifics of the excess holdup distribution along the cascade stages has been identified, and variations of the isotope concentrations in a nonstationary process have been revealed. The data obtained show that the proposed mathematical model is able to adequately describe nonstationary hydraulic processes in GC cascades for separation of multicomponent isotope mixtures.

Highlights:

Mathematical model of cascade for separation of multicomponent isotope mixture has been developed.

The model verification has been done.

The isotope transient regularities into cascade during nonstationary processes has been identified.     

Bromate Surveys in French Drinking Waterworks

Two bromate surveys were made recently in order to evaluate the frequency of bromate appearance in drinking waters issued from waterworks including one or two ozonation steps. The First survey was carried out on 47 waterworks. Two sampling campaigns were analyzed in cool and warm seasons. The objective of the second survey was to follow, during 4 to 10 months, at 12 selected waterworks.

The aim of this paper is to present the data obtained and to try to model for some waterworks the bromate formation by means of some important parameters (Br, O₃/DOC, T° and pH) of water to ozonate.

The main conclusion is that the bromate presence in distributed drinking waters is a reality for waterworks using ozonation steps, especially in warm period of the year. In the case of some waterworks, disinfection by sodium hypochlorite increased bromate levels in distributed water.

As shown by others on a laboratory-scale level, a multi-linear regression allows us the prediction of the bromate formation from some determining parameters, for some waterworks. However, the poor values of the linear regression lead us to have some doubts about its universal application in the real situation of an operating waterworks. A better evaluation of “C.t” will be required in the future in order to get a better prediction by the use of multi linear regression.     

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.     

ANALYSIS OF BISTABLE AND OSCILLATING REACTION SYSTEMS IN PRESENCE OF AN EXTERNAL NOISE

The paper analyses a bistable and an oscillatory reaction system in the presence of an external noise. The analysis of a bistable system shows that in the normal way the inclusion of noise destroys all the deterministic solutions. In other words, the stochastic system does not admit any solution. With imposition of certain restraints it is possible, however, to get stochastic solutions in a certain region of parameter space, which in general shrinks with the extent of noise. The modality of diminishing the region of solutions is different for white and nonwhite noise and has been discussed

The paper also evaluates the influence of white and nonwhite noise on the behavior of an oscillating system and illustrates it by considering two case examples. One example indicates the conflicting role of white and nonwhite noise in bringing about the transitions from the oscillatory behavior while the second example shows no influence of white and nonwhite noise on the oscillating solution

The implications of the role of noise in analysing bistable and oscillatory systems is discussed.     

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.     

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