Paliva (Fuels) is a scientific journal issued quarterly by the Faculty of Environmental Technology, ICT Prague. Fuels publishes papers on a broad range of topics covering exploitation, processing, upgrading, and utilization of various types of fuels, and power engineering.
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Phase transformation of the corrosion layers on nu-clear fuel cladding. Raman spectroscopy study.

Kryštof Frank, Ladislav Lapčák, Jan Macák

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.

4/2021 - pages 113 - 117DOI: 10.35933/paliva.2021.04.01

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

David Dašek, Petr Roztočil, Jan Macák
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.
Keywords: Recognition of kinetic transient process in corrosion scales of fuel elements by impedance spectroscopy
4/2021 - pages 118 - 122DOI: 10.35933/paliva.2021.04.02

Gas desulfurization adsorption technology

Karel Ciahotný
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.
4/2021 - pages 123 - 130DOI: 10.35933/paliva.2021.04.03

Stability of the pyrolysis condensates during their high-temperature treatment

Marek Staf, Michael Pohořelý, Siarhei Skoblia, Zdeněk Beňo, Vít Šrámek
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.
4/2021 - pages 131 - 140DOI: 10.35933/paliva.2021.04.04

Influence of sample preparation process on basic properties of biofuels

Hana Lisá, Martin Lisý, Patrik Elbl, Marek Baláš, Tereza Zlevorová, Miloš Matúš

The characteristic properties of non-wood biomass used in combustion processes are monitored, such as wa-ter content, ash, volatile matter. Biomass is usually not homogenous and of suitable dimensions for these deter-minations. 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 sam-ples 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.

4/2021 - pages 141 - 148DOI: 10.35933/paliva.2021.04.05

technical support editor-in-chief