Phase transformation of the corrosion layers on nuclear fuel cladding. Raman spectroscopy study.

The goal of this work was the phase analysis of corrosion layers on zirconium alloys. In the environment of nuclear reactors, zirconium alloys are covered with a protective layer of zirconium oxide, which occurs in two crystalline modifications - monoclinic and tetragonal. The distribution of these phases in the corrosion layer can affect the overall corrosion rate. Raman spectroscopy was used to determine the composition of the corrosion layers. The use of this method is advantageous because the monoclinic and tetragonal phases can be easily distinguished in the spectra of the corrosion layers. In total, samples of two alloys were measured. The samples were pre-exposed at 360 °C in Li+ containing water (70 mg/l Li as LiOH) . Exposure times were between 21 d and 231 d, so the series contained both pre- and post- transition samples. The relative proportion of the tetragonal phase decreases significantly after the transient. It has also been found that the corrosion layers are highly heterogeneous in terms of the distribution of crystalline modifications.

Stability of pyrolysis condensates during their high-temperature treatment

As part of a project dealing with the material use of waste plastics processed by pyrolysis, a method for the purification of primary pyrolysis gas at temperatures above the dew point of condensing components was proposed. In order to avoid the loss of liquid products, two procedures have been proposed to study this issue. The first procedure consists in separating the pyrolysis condensate from permanent gases and its subsequent evaporation and introduction into a high-temperature reactor where the purification takes place. The second procedure used the same equipment, but the pyrolyser was connected in series with a high temperature reactor by a heated tube. The function of the device is demonstrated on a pair of pure polymers, namely highdensity polyethylene and polypropylene. In practice, however, the device is used for testing waste plastics. The mass balance of liquid, gaseous and solid products of pyrolysis and subsequent vapour phase conduction through a high-tem-perature reactor was supplemented by data from chromatographic analysis. Experiments have shown that the separation of pyrolysis and subsequent evaporation of the condensate in an independent reactor causes the formation of an undesirable amount of fine aerosol (mist). Pyrolysis without any subsequent high-temperature step produced 85–90 % condensate. The inclusion of a separate high-temperature reactor reduced the yield of condensate to 44.5–47.5 %, at the expense of the above-mentioned mist. Its conver-sion back to liquid is difficult and makes the process inefficient for industry. In tests with the series-connected pyrolyser and the high-temperature reactor, the situation was significantly better. 68.5–73.5 % of condensate was obtained in this case. In addition to the formation of mist, the conduction of steam of condensing components through the high-temperature reactor also caused a slight change in the composition of the liquids obtained. There was a decrease in the proportion of C21–C29 hydrocarbons in products and, conversely, an increase in the concentration of C5–C15 hydrocarbons. Besides verifying a suitable approach to the high-temperature processing of pyrolysis products, the experiments showed that changing a single subparameter (in this case the separation of the two reactors) significantly altered the results of the experiments. During laboratory simulation of industrial processes, it is important not to approach simplifications, but to copy all conditions as much as possible.

Recognition of kinetic transient process in corrosion scales of fuel elements by impedance spectroscopy

The presented study concerns with the corrosion kinetics of two zirconium alloys: Zr-Nb-Sn-Fe and Zr-Nb-Fe. Alloy samples were pre-exposed at 360 °C in a LiOH solution containing 70 mg/l of lithium ions. Ex-situ electrochemical impedance spectroscopy (EIS) performed in 0.5 M potassium sulphate solution at 25 °C was used to study the properties of the oxide and kinetic transient effect. Evaluation of the impedance spectroscopy data was based on application of a simple equivalent circuit. The setup of the equivalent circuit conformed to Jonscher´s universal law of dielectric response. The analysis of the impedance data was aimed at estimation of non-dispersive capacitance of the oxide formed during the pre-exposure. Effective values of dielectric constant were calculated using the non-dispersive capacitance and the oxide thickness values, calculated from weight gains. For the pre-transient samples relatively higher values of dielectric constants were obtained. Typical pre-transient dielectric constants for Zr-Nb-Sn-Fe alloy ranged between 20–21, while slightly lower values were obtained for Zr-Nb-Fe alloy. In both alloys steep and significant decrease in effective dielectric constant (e_ef = 9–13) was found for the transient samples. The decrease correlated very well with the drop in percentage of tetragonal oxide determined by Raman spectroscopy and corresponded to the increase of the weight gains of the transient samples. Literature data indicate values of dielectric constants for tetragonal zirconium oxide between 38–46, while those for monoclinic oxide are usually presented between 12–22. The evidenced changes in dielectric constants are therefore in agreement with the expected decrease of tetragonal phase fraction in the oxide layer during the transient. In the Zr-Nb-Sn-Fe post-transient samples values of dielectric constant increased again to 18–20, therefore almost to the pre-transient level. This increase was not evidenced with Raman spectroscopy data, which show constant low content of the tetragonal fraction. Possible explanation of this disagreement is the location of the newly formed post-transient tetragonal oxide presumably at the metal/oxide interface. Oxide thickness of the post-transi-ent samples is 4–7 m and the oxide/metal interface is beyond access of the laser beam of Raman spectrometer. We can conclude that using ex-situ EIS, the transient was observable in both alloys; the change in the ratio of monoclinic and tetragonal phase can be evaluated based on the difference of effective dielectric constant of the two phases. The Zr-Nb-Sn-Fe alloy showed the onset of the transient after the 105th day of pre-exposure, but the change in the ratio of the monoclinic and tetragonal phases was less significant than in the Zr-Nb-Fe alloy, in which, however, the transient could be observed only after 147 days of pre-exposure. The resulting values of the effective dielectric constant of oxides correlated well with the percentage of tetragonal oxide determined by Raman spectroscopy and with the results of the weight gain method.

Influence of sample preparation process on basic properties of biofuels

The characteristic properties of non-wood biomass used in combustion processes are monitored, such as water content, ash, volatile matter. Biomass is usually not homogenous and of suitable dimensions for these determinations. This is the reason for the necessary adjustment of samples for analysis. But modifying the samples may change their properties. In this publication, the influence of the grinding process in a rotor mill on the content of water, volatile matter and ash in non-wood biomass samples was studied. Samples of flax, Crambe abyssinica, amaranth and rye were analyzed. All analyses showed moisture loss from the sample during grinding and in the case of flax, the loss of volatile matter was observed. It means the rotor mill is suitable for sample preparation prior to analysis. But for oil plants it is necessary to choose another mill or adjustment method.

Gas desulfurization adsorption technology

Adsorption technologies used for gas desulfurization are a widespread technique which, due to its relative simplicity, are widely used to the purification smaller volumes of gas. However, for their trouble-free and economical use, it is necessary to respect several basic requirements for the selection of suitable types of adsorbents with respect to the specific composition of the purified gas. The article provides a brief overview of the history of the development of adsorption technologies and also provides several different examples of the operational use of this technology for the purification of gases containing high concentrations of sulfur substances. Furthermore, the principles of correct selection of a suitable adsorbent for specific application cases are also specified here. Iron oxide adsorbents were used in the early times of the operation of the technology, which were inexpensive but had a relatively low sorption capacity for sulfur compounds. Therefore, sorbents based on iron oxides have been gradually replaced by more powerful, but also more expensive sorbents based on activated carbon. Initially, activated carbon without impregnation was used, the production of which took place in the Czech Republic on an industrial scale. By the further development of impregnated types of activated carbon and their introduction into industrial production, these adsorbents have been also used in adsorption technologies intended for gas desulfurization. Their sorption capacity is much higher in comparison with non-impregnated types of activated carbon, because the impregnants used convert sulfur compounds from gas into non-volatile substances (elemental sulfur, sulfides, polysulfides). This ensures a long service life of the adsorbent and high efficiency of gas purification from sul-fur substances.

Low-cost natural carbon dioxide sorbents available in the Czech Republic

The article deals with the issue of carbon dioxide adsorption on mineral samples, two of which are rich in montmorillonite and one in kaolinite. The last comparative sample is clinoptilolite, which is widely used as a sorbent in agriculture, water treatment, etc. The theoretical part summarizes several current researches on the use of bentonites as adsorbents, both in their raw form and after various chemical treatments. The study presented here does not suggest any modification procedure, but tests untreated samples and samples subjected to calcinations at temperatures of 250-750 ° C. The calcination of units of grams was carried out by means of a carousel TGA, which made it possible to record curves of mass changes and to obtain a sufficient amount of calcinates for further analyses at the same time. From the point of view of achieving the highest specific surface area and the total pore volume, the optimal calcination temperature for the phyllosilicate samples ranged from 250 to 450 °C. Natural zeolite, on the other hand, showed a deterioration of both of these parameters at any temperature exceeding 150 °C. The same temperature dependence was found in the case of adsorption capacities determined by an automatic analyser Autosorb IQ using pure CO2. Measurements on this instrument also confirmed that selected inexpensive natural materials provide comparable adsorption capacities as the commercially available 13X molecular sieve used as a reference sample. Based on the performed analyses, the initial conditions of sample preparation for the upcoming measurement of adsorption properties on a larger apparatus operating in the PSA/TSA mode were determined. The primary aim of the tests using the selfdesigned high-pressure adsorption unit will be to determine the adsorption capacities that will take into account the temperature and pressure conditions in a real postcombustion carbon dioxide capture system. Unlike the automatic analyser described above, it will be possible to quantify the influence of important factors such as: flue gas humidity, the presence of other permanent gases (especially SO2) and last but not least various CO2 partial pressures and absolute pressure during adsorption and desorption. The experiments will verify the extent to which the presence of noncondensing moisture in the gaseous mixture is problematic. In the case of phyllosilicates, it is not just the parallel adsorption of H2O that affects the adsorption capacity available for CO2 capture. It will be empirically determined to what extent the swelling of the sorbent occurs in the wet gas, changing the gas flow through the layer and especially the pressure loss. The results of measurements on high-pressure apparatus will be the basis for the design and construction of a larger pilot scale unit.

A mathematical model of relation and origin of variation between CRI and CSR indexes

The aim of this work is both the mathematical relation and the value variation analysis between CRI and CSR indexes. For this aim the physical mathematical model is proposed on the basis of the ISO-test. The physical basis of the model is a material balance of a one piece of coke from the ISO sample. Results of calculating by the model are curves of CSR=f(CRI) which reproduces the regressions in analogy with CSR=a+b.CRI for most coke-producing countries. The model showed that a larger part of CSR=f(CRI) curve is linear and that a universal regression in analogy with CSR=a+b.CRI does not exist. As follows from the model, every piece of coke from the ISO sample has its own CSR=f(CRI) curve with a CRI and CSR point. Between pieces of coke, variations of CRI and CSR values can be explained by the open pore amount, the coke pores’ surface area, the statistical distribution of molecular oriented domains on the basis of Lc and the coke piece mass. In our results, pores with a geometrical orientation from the outside to the center of a coke piece and having a minimum length significantly influence on the coke quality according to CRI and CSR indexes.

Transformation of coal-fired power plants on steam-gas power plants

Currently in the EU there are bigger tendencies to reduce emissions of carbon dioxide and phasing out of coal mining and combustion. There are some possibilities to transform current coal-fired power plant to steam-gas one. The advantages of steam-gas power plant are lower amount of emissions and higher efficiency unlike coal-fired one and stability of energy production unlike wind and solar one. The article focuses on principle, description and ad-vantages of steam-gas power plant. It also mentions and compares methods of transformation current coal-fired power plant to steam-gas one. Finally, the possible expansion of these power plant in the Czech Republic is discussed, with regard to economic aspects and EU cli-mate change policy.

Impact of the anaerobic digestion process configuration on the sludge dewaterability

Anaerobic sludge digestion is an important tool for converting sludge into a renewable fuel - biogas. However, digested sludge can also be used as a fuel, and a fundamental parameter determining the energy value of digested sludge is as effective as possible dewatering. The main aim of the presented study was to evaluate how the anaerobic digestion (AD) technology and post-treatment technology can affect sludge dewaterability. Two technological alternatives of AD were evaluated: mesophilic (MAD) and thermophilic (TAD). In addition, also the effect of postaeration of digested was evaluated. The dewaterability was assessed using two methods based on centrifugation and filter pressing. Finally, the sludge cake concentration of total suspended solids (TSS) was compared. The results showed the difference in sludge dewaterability for the tested sludges: The sludge cake concentration was similar or slightly higher for MAD compared to TAD sludge. Post-aeration of digested sludge increased sludge cake concentration.

Sulfint – the Czech gas desulfurization technology

The article describes one of the gas desulphurisation technologies which has been developed in the Czech Republic. The technology uses washing solution of organic complexes of various metals to remove H2S from gases. H2S removal is realized by its reaction with complexes of suitable metals with organic reagents. This leads to the H2S oxidation to elemental sulfur and the reduction of the metal protected by the organic complex to a lower oxidation state, which is also bound in the organic complex. Regeneration of the washing solution is performed by oxidation of the reduced form of the complex using oxygen from the air. Complexes of iron with ethylenediaminetetraacetic acid, nitrile triacetic acid or diethylenetriaminopentaacetic acid are used for the preparation of washing solutions. The reaction of the ferric complex of ethylenediaminetetraacetic acid with H2S is accompanied by a change in the color of the washing solution from a deep red color (like red wine) to a light brown color (like coffee with milk) of the ferrous complex of ethylenediaminetetraacetic acid. When this complex is completely depleted, it begins to decompose to black ferrous sulfide by further contact with H2S. This reaction is irreversible. The ferrous complex of ethylenediaminetetraacetic acid can be regenerated by reaction with oxygen, which also takes place at normal or elevated temperatures. The rate of this reaction is much slower compared to the reaction of H2S with the ferric complex. The process was discovered and intensively researched at the Institute for Fuel Research in Prague and later also at the University of Chemistry and Technology Prague. The first pilot plant tests took place with the desulfurization of coke oven gas at the Coking Plant Vítězný únor in Ostrava, where the first operating facility working with the given technology was later built. Another operating facility working with this technology was put into operation at the Antonín Zápotocký High pressure gasification plant in Ústí nad Labem and was used for desulphurization of expansion gases from pressure purification of waste gas of the Rectisol system. The technology was named Sulfint. Both facilities operated successfully until the end of operation of the town-gas supply system in the Czech Republic in the mid-1990s.