The paper focuses on the modelling of bromate formation. An axial dispersion model was proposed to integrate the non-ideal mixing, mass-transfer and a kinetic model that links ozone decomposition reactions fromthe Tomiyasu, Fukutomi and Gordon (TFG) ozone decaymodelwith direct and indirect bromide oxidation reactions, oxidation of natural organicmatter and its reactionswith aqueous bromine. To elucidate the role of ammonia an additional set of reactions leading to bromamine formation, oxidation and disproportionation was incorporated in the kinetic model. Sensitivity analysis was conducted to obtain information on reliability of the reaction rate constants used and to simplify the model.
Validation results of a theoretical model that describes the formation of bromate during ozonation of bromide-containing natural waters are presented. An axial dispersion model integrating the nonideal mixing, mass-transfer and a kinetic model that links ozone decomposition reactions from the Tomiyasu, Fukutomi and Gordon ozone decay model with direct and indirect bromide oxidation reactions, oxidation of natural organicmatter and reactions of dissolved organics and aqueous bromine was verified. Themodel was successfully validated with results obtained both at a laboratory and a full scale. Its applicability to different water supply systems was approved.
The quantitative description of an airlift bioreactor, in which aerobic biodegradation limited by carbonaceous substrate and oxygen dissolved in a liquid takes place, is presented. This process is described by the double-substrate kinetics. Mathematical models based on the assumption of plug flow and dispersion flow of liquid through the riser and the downcomer in the reactor were proposed. Calculations were performed for two representative hydrodynamic regimes of reactor operation, i.e. with the presence of gas bubbles only within the riser and for complete gas circulation. The analysis aimed at how the choice of a mathematical model of the process would enable detecting the theoretical occurrence of oxygen deficiency in the airlift reactor. It was demonstrated that the simplification of numerical calculations by assuming the “plug flow” model instead of dispersion with high Péclet numbers posed a risk of improper evaluation of the presence of oxygen deficiency zones. Conclusions related to apparatusmodelling and process design were drawn on the basis of the results obtained. The paper is a continuation of an earlier publication (Grzywacz, 2012a) where an analysis of single-substrate models of the airlift reactor was presented.
The cometabolic biodegradation of 4-Chlorophenol (4-CP) by the Stenotrophomonas maltophilia KB2 strain in the presence of phenol (P) was studied. In order to determine the kinetics of biodegradation of both substrates, present alone and in cometabolic systems, a series of tests was carried out in a batch reactor changing, in a wide range, the initial concentration of both substrates. The growth of the tested strain on phenol alone was described by Haldane kinetic model (mm = 0:9 1/h, Ksg = 48:97 gg/m3, KIg = 256:12 gg/m3, Yxg = 0:5715). The rate of 4-CP transformation by resting cells of KB2 strain was also described by Haldane equation and the estimated parameters of the model were: kc = 0:229 gc=gxh, Ksc = 0:696 gc=m3, KIc = 43:82 gc=m3. Cometabolic degradation of 4-CP in the presence of phenol was investigated for a wide range of initial 4-CP and phenol concentrations (22–66 gc/m3 and 67–280 gg/m3 respectively). The experimental database was exploited to verify the two kinetic models: CIModel taking only the competitive inhibition into consideration and a more universal CNIModel considering both competitive and non-competitive inhibition. CNIModel approximated experimental data better than CIModel.
In order to investigate the mechanism of adsorption of reactive dyes from the textile industry on ash from heating plant produced by brown coal combustion, some characteristic sorption constants are determined using Langergren adsorption equations for pseudo-ﬁ rst and pseudo-second order. Combined kinetic models of pseudo-ﬁrst order and pseudo-second order can provide a simple but satisfactory explanation of the adsorption process for a reactive dye. According to the characteristic diagrams and results of adsorption kinetic parameters of reactive dyes on ashes, for the applied amounts of the adsorbents and different initial dye concentrations, it can be concluded that the rate of sorption is fully functionally described by second order adsorption model. According to the results, the rate constant of pseudo-second order decreases with increasing initial dye concentration and increases with increasing amount of adsorbent – ash.
Steel is a versatile material that has found widespread use because of its mechanical properties, its relatively low cost, and the ease with which it can be used in manufacturing process such as forming, welding and machining. Regarding to mechanical properties are strongly affected by grain size and chemical composition variations. Many industrial developments have been carried out both from the point of view of composition variation and grain size in order to exploit the effect of these variables to improve the mechanical proprieties of steels. It is also evident that grain growth are relevant to the mechanical properties of steels, thus suggesting the necessity of mathematical models able to predict the microstructural evolution after thermo cycles. It is therefore of primary importance to study microstructural changes, such as grain size variations of steels during isothermal treatments through the application of a mathematical model, able in general to describe the grain growth in metals. This paper deals with the grain growth modelling of steels based on the statistical theory of grain growth originally developed by Lücke  and here integrated to take into account the Zener drag effect and is therefore focused on the process description for the determination of the kinetics of grain growth curves temperature dependence.
Measurements of the hardening process of the selected self-setting sands are presented in the hereby paper. Moulding sands were prepared on the matrix of „Szczakowa” sand of the Sibelco Company. Two resins: phenol-formaldehyde-furfuryl (FF/AF) and urea-formaldehydefurfuryl (MF/AF) were used for making moulding sands. – Methylbenzene-sulphonic acid was applied as a hardener for the moulding sand on FF/AF resin, while paratoluene-sulphonic acid for the moulding sand on MF/AF resin. Both hardeners were used in two concentrations: low – the so-called ‘slow’ hardener and high - ‘fast’ hardener. During investigations, the courses of the hardening process were determined, more accurately changes of the velocity of the ultrasound wave passage through the moulding sand cL = f(t) and changes of the moulding sand hardening degree versus time, Sx = f(t). In addition, the kinetics of the hardening process was determined. Measurements were performed on the research stand for ultrasound investigations.
Measurements of the hardening process course of the selected self-hardening moulding sands with the reclaimed material additions to the matrix, are presented in the hereby paper. Moulding sands were produced on the „Szczakowa” sand (of the Sibelco Company) as the matrix of the main fraction FG 0,40/0,32/0,20, while the reclaim was added to it in amounts of 20, 50 and 70%. Regeneration was performed with a horizontal mechanical regenerator capacity of 10 t/h. In addition, two moulding sands, one on the fresh sand matrix another on the reclaimed matrix, were prepared for comparison. Highly-fluid urea-furfuryl resin was used as a binder, while paratoluensulphonic acid as a hardener. During investigations the hardening process course was determined, it means the wave velocity change in time: cL = f(t). The hardening process kinetics was also assessed (dClx/dt = f(t)). Investigations were carried out on the research stand for ultrasound tests. In addition strength tests were performed.
The aim of this article is to present a modern method of convective drying intensification caused by the external action of ultrasound. The purpose of this study is to discover the mechanism of ultrasonic interaction between the solid skeleton and the moisture in pores. This knowledge may help to explain the enhancement of drying mechanism affected by ultrasound, particularly with respect to biological products like fruits and vegetables. The experimental kinetics tests were conducted in a hybrid dryer equipped with a new ultrasonic generator. The drying kinetics curves determined on the basis of drying model developed by the author were validated with those by the ones obtained from experimental tests. The intensification of heat and mass transfer processes due to ultrasound induced heating effect and vibration effect are analysed. The obtained results allow to state that ultrasound makes drying processes more effective and enhance the drying efficiency of biological products without significant elevation of their temperature.
Ludwigite is the main available boron-bearing resource in China. In order to enrich the theory system and optimize its utilization processes, this paper study the mechanism and kinetics on non-isothermal decomposition of ludwigite in inert atmosphere by means of thermal analysis. Results show that, the decomposition of serpentine and szajbelyite is the main cause of mass loss in the process. At the end of decomposition, hortonolite and ludwigite are the two main phases in the sample. The average E value of structural water decomposition is 277.97 kJ/mol based on FWO method (277.17 kJ/mol based on KAS method). The results is proved to be accurate and reliable. The mechanism model function of structural water decomposition is confirmed by Satava method and Popescu method. The form of the most probable model function is G(α) = (1 – α)–1 – 1 (integral form) and f (α) = (1 – α)2 (differential form), and its mechanism is chemical reaction. This is verified by the criterion based on activation energy of model-free kinetics analysis.
The main goal of the presented work was to determine the relationship between changes in the shape of the derivative curve and the microstructure of Zn-Al-Cu alloys before and after modification. To describe the phenomena that occur in the material during solidification as a result of the modification in the chemical composition, the thermal-derivative analysis method was applied. This method allows to describe and interpret the kinetics of crystallisation of the tested alloys. To describe the morphology and phase composition, light and electron microscopy (SEM, TEM) was also used. The modification of the hypereutectic Zn-Al-Cu alloys with the addition of Ce causes a reduction in the size α' + η eutectics and change in the morphology of the α' phase precipitates from dendritic to “tweed”.
This work presents the qualitative and quantitative changes in the products of isothermal transformation (reaction) in a ductile cast iron austenite after supercooling to the temperature range Ar1. The austenitizing temperature considered in this work was 900, 960 or 1020°C. The eutectoid reaction was investigated by metallographic examination at a holding temperature right below Ar11 (820°C) or right below Ar12 (760°C). The quantitative metallographic examination was carried out with a light microscope (LM). The initial transformation stage products were identified with a transmission electron microscope (TEM). The selected samples were studied for chemical microsegregation of manganese, silicon, phosphorus, and carbon with an X-ray microanalyser (MAR). The tested cast iron material was found to predominantly feature a eutectoid reaction in the metastable system the ratio of which was increasing with the austenitizing temperature. The austenitizing temperature was found to be conducive to the evolution kinetics of individual phases and to the graphitization kinetics of the eutectoid cementite that was formed during the contemplated reaction.
A catalytic combustion of organic admixtures of air belongs to the basic technologies of gas purification. A macrokinetics of admixtures combustion over the porous catalysts was described. The theoretical approach is in agreement with standard description of macrokinetics of the catalytic processes. The relationship between the fundamental magnitudes: observed process rate r*, reaction rate r in the kinetic zone, and a coefficient of the surface utilization η in the form r*= r · η have been described. These magnitudes combines the Thiele module φ. A kinetics equation for the isothermal and non-isothermal conditions was provided. The influence of mass and heat transfer in the catalyst grain on the course of the process was described by means of the surface utilization coefficient η. An equation describing this coefficient for both isothermal and non-isothermal conditions was given. The second part of this work concerns the application of theory. When the composition of purified gas is continuously varied, a quantitative approach is rather impossible. The theory was used for the qualitative analysis of process on the basis of the experimental results. A fulfillment of the first-order kinetics means that the degree of admixtures conversion does not depend on their initial concentrations. A non-isothermicity of the catalyst grain is expressed in such a way that the process rate observed over the large porous grains of the catalyst can be higher than the reaction rate in the kinetic zone. A temperature deference between the catalyst grains and flowing gas causes that the reactor can be stably operated at varied concentrations of admixtures and temperature over a relatively wide range. It was also demonstrated that the flammable admixtures may advantageously influence the conversion of hardly combustible admixtures
The paper presents results of research on cobalt and nickel ions removal from monocomponent solutions using Purolite ion exchange resins. It has been shown that C 160 ion exchange resin has the best sorption properties for both ions (Qe – 72.5 mg Co/g and 88.2 mg Ni/g). Regeneration process of this ion exchanger has high efficiency, achieving about 93% for cobalt ions and about 84% in case of nickel ions. It has been shown that the use of ion exchange method with suitable ion exchange resins guarantees effective removal of cobalt and nickel ions from solutions with very high concentrations corresponding to contents of these metals in industrial wastewaters (e.g. galvanic). In case of C 160 ion exchange resin, after the sorption process is carried out in one 50 minute cycle, the cobalt concentration decreased from about 30 000 mg/L to about 9 500 mg/L (approx. 68%), whereas nickel concentration reached about 6 300 mg/L (approx. 79%). Studied chelating resins don’t have such high sorption capacities. In their case, it is required to convert cobalt and nickel ions into complex forms. The kinetics of studied processes were described by pseudo-second order equations.
The extracellular polymeric substance (EPS) produced from Rhizobium radiobacter F2, designated as EPSF2, was investigated as a biosorbent for the removal of Pb(II) and Zn(II) from aqueous solution. The optimum biosorption pH values were 5.0 for Pb(II) and 6.0 for Zn(II). Kinetics study revealed that the biosorption followed pseudo-first-order model well, and the equilibrium data fit the Langmuir model better. The adsorbed metal ions could be effectively desorbed by HCl. Desrobed EPSF2 regained 80% of the initial biosorption capacity after five cycles of biosorption-desorption-elution. These results demonstrated that EPSF2 could be a promising alternative for Pb(II) and Zn(II) removal from aqueous solution.
Gas emission from casting moulds, cores and coatings applied for sand and permanent moulds is one of the fundamental reasons of casting defects occurrence. In the previous studies, gas emission was measured in two ways: normalized, in which the evolving gas volume was measured during heating of the moulding sand sample in a sealed flask, or by measuring the amount of gas from sand core (sample) which is produced during the pouring of liquid metal. After the pouring process the sand mould is heated very unequally, the most heated areas are layers adjacent to the liquid metal. The emission of gas is significantly larger from the surface layer than from the remaining ones. New, original method of measuring kinetics of gas emission from very thin layers of sand moulds heated by liquid metal developed by the authors is presented in the hereby paper. Description of this new method and the investigation results of kinetics of gas emission from moulding sand with furan and alkyd resin are shown. Liquid grey cast iron and Al-Si alloy were used as a heat source in the sand moulds. Comparison of the kinetics of gas emission of these two kinds of moulding sands filled with two different alloys was made. The momentary metal temperature in sand mould was assigned to the kinetics of gas emission, what creates a full view of the possibility of formation of casting defects of the gaseous origin. Moulding sand with alkyd resin is characterized by larger gas emission; however gases are emitted slower than in the case of moulding sands with furan resin. This new investigation method has a high repeatability and is the only one which gives a full view of phenomenon’s in the surface layer which determines quality of the casings. The obtained results are presented on several graphs and analyzed in detail. They have a great application value and can be used in the production of iron as well as light metal alloy castings.
The growth kinetics of the zinc coating formed on the surface of casting made from ductile iron grade EN-GJS-500-3 was investigated. To produce homogenous metal matrix in test samples, the normalising and ferritising annealing was carried out. Studies showed a heterogeneous structure of cast iron with varying content of the phases formed. This was followed by hot dip galvanising treatment at 450°C to capture the growth kinetics of the zinc coating (the time of the treatment ranged from 60 to 600 seconds). Nonlinear estimation of the determined growth kinetics of the alloyed layer of a zinc coating was made and an equation of the zinc coating growth was derived. Based on the results of the investigations it was concluded that thickness of the zinc coating formed on the surface of casting with a 100% pearlitic matrix makes 55% of the thickness of coating formed on the surface in 100% ferritic.
This scientific paper presents the research on influence of austenitizing temperature on kinetics and evolution of the spheroidal plain cast iron during eutectoid reaction in isothermal conditions. The cast iron has been austenitized in temperatures of 900, 960 or 1020°C. There were two temperature values of isothermal holding taken into consideration: 760 or 820°C. The order of creation of reaction products and their morphology have been analyzed. The particular attention has been paid to the initial stage of transformation. The qualitative research has been executed using the transmission electron microscope (TEM), as well as quantitative research (LM). The influence of austenitizing temperature has also been determined on transformation kinetics and structural composition. It was found that the increase of austenitizing temperature is conductive to the initial release of structures by metastable system. A reduction of time was observed of the initial stage of transformation at temperature close to Ar12 with its simultaneous elongation at temperature close to Ar11, with an increase of austenitizing temperature. The dependences obtained by the metallographic method confirm the prior results of dilatometric research of eutectoid reaction.
Zinc is present in electric arc furnace dust (EAFD) mainly in two basic minerals, namely as franklinite ZnFe2O4 and/or zincite ZnO. While zincite is relatively reactive and easily treatable, franklinite is considerably refractory, which causes problems during EAFD processing. In this work EAFD containing 18.53% Zn was leached in water solution of ammonium carbonate. This leaching solution selectively leaches zincite, while franklinite is refractory and stable against leaching in this case. The temperature dependence of zinc leaching from EAFD was studied and the activation energy EA was determined by two methods: 1.) classically based on zinc chemical analyses from the leaching solution and 2.) by using of X-Ray diffraction qualitative phase analyses of leaching residues. The determined values of activation energies 37.41 and 38.55 kJmol–1 match perfectly, which show the excellent possibility of using X-Ray diffraction toward the study of leaching kinetics at properly chosen experimental conditions. The important result is the determination of the amount zincite and franklinite in EAFD, which is not possible by using of classical chemical methods.