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Electric characteristics of the diaphragm discharge in electrolyte solutions
Dřímalková, Lucie ; Slavíček, Pavel (referee) ; Kozáková, Zdenka (advisor)
The main object of this thesis is the diagnostics of the diaphragm discharge generated in water solutions containing supporting electrolytes (mostly NaCl), and description of particular processes before and after discharge breakdown by DC non-pulsed voltage up to 2 kV. Although many applications of electric discharge in liquids have been developed during the last years, the exact mechanism of the discharge ignition is not sufficiently known up to now. Based on this reason, this work is focused on the investigation of processes before the discharge ignition, breakdown parameters and the discharge itself both in the irregular and stable regime. The theoretical part of the work presents proposed mechanisms of the discharge generation in water solutions including the description of particular kinds of known discharges. Diaphragm discharge is one of many possible configurations of electrical discharges in liquids. In fact, electrical discharge in water forms non-thermal plasma, which is generated by high voltage, and many physical and chemical processes are started in plasma channels (so-called streamers). Among physical processes, high electrical field, shock waves and last but not least emission of electromagnetic radiation in visible and ultra-violet radiation belongs. The most important chemical processes are generation of various active species as hydrogen peroxide, and OH radical. Three batch plasma reactors using a diaphragm configuration with different total volume (4 l, 100 ml and 50 ml) are employed in the presented work. The discharge is created in an orifice (a pin-hole) in the dielectric barrier separating two electrode parts of the reactor. DC non-pulsed high voltage up to 4 kV is used for the discharge generation. Electrodes are made of stainless steel or platinum, and they are installed in parallel to the diaphragm in a variable distance from the dielectric barrier in each reactor part. The dielectric barrier is made of PET or Shapal-MTM ceramics with the variable thickness (0.2?2 mm). One pin hole st the diaphragm center with diameter of 0.2?1.5 mm are used in contemporary experiments. Time resolved characteristics of current and voltage are recorded using four-channel oscilloscope which detected their output values. Parameters are measured by the constantly increasing DC voltage with a step of 100 V. The solutions containing sodium chloride electrolyte are used at five different conductivities. Recorded time resolved characteristics determine breakdown moment, and describe current and voltage in particular parts within the static current-voltage curve. The breakdown appeared at lower applied voltage when the electrode distance is enhanced. However, the electrode distances higher than 4 cm does not induce any significant change of the breakdown voltage. The influence of pin-hole diameter is less obvious in the studied range, but a slight enhancement of breakdown voltage is observed with the increasing pin-hole diameter. Current-voltage characteristic curve moves towards lower voltage with the diaphragm thickness enhancement. The work compares the influence of conductivity change on current-voltage characteristics as well as the effect of inorganic salt kind. By the conductivity enhancement, the measured current-voltage curve moves towards lower voltage which means that the breakdown voltage is decreased. Sizes of the reactors do not have any effect on the processes before and after discharge breakdown.
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Diaphragm discharge in organic dye solutions
Pajurková, Jana ; Možíšková, Petra (referee) ; Kozáková, Zdenka (advisor)
This Diploma thesis was focused on the degradation of dyes Saturn Red L4B (Direct Red 79) and Saturn Blue LB (Direct Blue 106) by DC diaphragm discharge (DC-DD). Supplied power was between 160 and 180 W. Conductivity and pH were changing at each electrode area during the DC diaphragm discharge, therefore the effect of pH and conductivity changes on the dye solution itself were examined. All samples were measured by UV-VIS spectrometer in the wavelength range of 300–800 nm. No significant dependence of dye absorption spectra on conductivity was observed, while pH significantly affected the absorption curves of dyes. Ageing of dye spectra showed significant changes of Saturn Red L4B. Next task was the comparison of dyes destruction efficiency by DC-DD, audiofrequency diaphragm discharge (AF-DD) and electrolysis. Dye decomposition by AF-DD was not observed at set conditions (voltage of 80–120 V, current of 2.2 A and frequency of 2 kHz). In the case of DC diaphragm discharge the electrolysis played an important role. Decomposition efficiency of the dyes by electrolysis was up to 15 %. The pumping effect in the DC diaphragm discharge was also investigated. Although the individual electrode areas were linked only by a small pinhole in a nonconductive barrier (the pinhole diameter of 0.3 mm), solutions of the anode and cathode compartment interacted with each other up to 10 %. Finally, the degradation products of Saturn Red L4B treated by DC-DD in two electrodes parts are also described. Decomposition products were determined by high performance liquid chromatography (HPLC) combined with the mass spectrometer.
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Diaphragm discharge in organic dye solutions with focus on electrolytic decomposition
Davidová, Jaroslava ; Brablec, Antonín (referee) ; Kozáková, Zdenka (advisor)
This Diploma thesis is focused on physical and chemical effects which contribute to the decomposition of organic dyes by diaphragm discharge generated in water solutions. Due to the application of DC high voltage source in continuous regime, there is an effect of electrolysis contributing to the dye decomposition by diaphragm discharge. The aim of this work was to find out when the electrolysis is running (or when is the moment of discharge breakdown) and which factors influence the breakdown. The other goal was decomposition of selected textile and food organic dyes by electrolysis itself. In the theoretical part, theory about creation of electrical discharges in aqueous solutions is noted and various types of underwater discharges are described. Background researches about underwater electrical discharges used in the world are mentioned as well as the use of diaphragm discharges and various ways how to remove organic dyes from wastewater. Finally, theories of electrolysis, UV-VIS spectroscopy and basis of other analytical methods useful for detection of organic molecules are described. Experimental part is oriented to experiment procedure which was carried out in a reactor with separated electrode areas. Separation was made by dielectric diaphragm with a pinhole in the centre. Its initial diameter was 0.4 mm. Used chemicals and course of experiments are described in this part, too. First, the breakdown moment in the reactor was investigated (i. e. determination, when only electrolysis was operating) by formation of hydrogen peroxide and measurement of dynamic (time resolved) electrical characteristics. Next, decomposition of selected dyes by electrolysis was carried out. As the decomposition was related to decolorization of the solution, UV-VIS spectroscopy in the range of 350–700 nm was used for determination of dye concentration. Next part focused on results presents various factors which had an effect on breakdown of diaphragm discharge. These factors are kind of used electrolyte, initial conductivity of solution, kind of dye, temperature of solution and type of reactor (or solution volume). From the result, the most important factor is initial solution conductivity. After the determination of the breakdown moment, the electrolysis of organic dyes was performed. The applied current was 10 mA, initial conductivity was 500 µS/cm and used electrolyte was NaCl. Moreover comparison of dye decomposition in dependence on the different applied power was realized. From this comparison one can assume, there is no significant contribution of electrolysis (the efficiency is approximately 15 %) to the diaphragm discharge in aqueous solution.
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Analysis of humic acids solutions after their decomposition by diaphragm discharge
Totová, Ivana ; Švejdová, Dana (referee) ; Kozáková, Zdenka (advisor)
Preliminary results of research focused on the applications of DC diaphragm discharge in water solutions containing humic substances are presented in this diploma thesis. Electrical discharges in water produce various reactive species such as radicals (•OH, •O, •H), ions and molecules (H2O2, O3). These species have high oxidation potential and thus they easily react with order species and molecules. Such reactions could lead, for example, to destruction of organic pollutants dissolved in water. This work studies this effect on humic matters that can be contained in water coming from floods. Diaphragm discharge investigated by this work was created in the reactor using konstant DC high voltage up to 2 kV that gave the total input power from 100 to 200 W. Breakdown and discharge ignition started in the pin-hole in the dielectric barrier separating two electrode spaces (anode and cathode space). Presented work investigates decomposition of humic substances by the electric discharge in the dependence of solution properties and discharge conditions. Parameters such as initial solution conductivity, electrolyte kind or input power have been investigated. Moreover, substantial effect of pH on humic acid decomposition has been observed. Refraktometry and absorption spectroscopy in UV-VIS region together with fluorescence spectroscopy has been used for the detection of changes in humic solutions.
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Study of electrolyte influence on diaphragm discharge stability and efficiency
Němcová, Lucie ; Krčma, František (referee) ; Kozáková, Zdenka (advisor)
This thesis is focused on so-called diaphragm discharge, which is one kind of electric discharges in liquid, which belongs among so-called AOP´s techniques, still more used for water cleaning in the present. One of effectiveness and stability indicators of diaphragm discharge is generation of hydrogen peroxide. In theoretical part, detail principle description of electric discharge in liquid is situated. Further, properties of electrolyte are introduced and general spectrophotometric method of obtained sample determination is described. In experimental part, a full procedure of experiment is introduced. Next part containing results and discussions introduces particular results of individual measurements and their reasons. Final chapter is the end, which forms total summary and evaluation of all results. By the application of all chosen electrolytes in solution at diaphragm discharge formation of hydrogen peroxide has appeared. Inorganic and organic electrolytes were used. As inorganic electrolytes following salts were selected – solutions of halogenides, next sodium nitrate as a representative of nitrates, potassium dihydrogenphosphate as a representative of phosphates, etc. Representative of organic electrolytes was citric acid. The value of initial conductivity of electrolytes had the main influence on hydrogen peroxide formation. Electrolytes potassium dihydrogenphosphate and sodium sulphate the great influence on effectiveness and stability of the diaphragm discharge. Their rate constants reached maximum value by the application of solution with initial conductivity of approximately 400 mikrosiemens, particularly 0.0492 mmol/l.min and 0.048 mmol/l.min. On the contrary, low values of rate constant were achieved in electrolyte ammonium chloride at around the same initial conductivity – 0.0269 mmol/l.min. During experiments stainless steel and platinum electrodes were used. It was found that kind of electrode material hadn’t influence on generation of hydrogen peroxide. Hydrogen peroxide was formed only in the cathode space.
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Diagnostics of diaphragm discharge in liquids
Dřímalková, Lucie ; Krčma, František (referee) ; Kozáková, Zdenka (advisor)
The main goal of this thesis is the diagnostics of the diaphragm discharge generated in liquids. Although many applications of electric discharge in liquids have been developed during the last years, the exact mechanism of the discharge ignition is not sufficiently known up to now. Based on this reason, this work focused on the investigation of processes before the discharge ignition, breakdown parameters and the discharge itself both in the irregular and stable regime. Using two kinds of inorganic salt solutions the work studied the influence of conductivity and electrolyte kind on the diaphragm discharge and its static current-voltage characteristics. The last task of the work investigated the emission spectra produced by the discharge. The theoretical part of the work presents mechanisms of the discharge generation in gases including the description of particular kinds of known discharges. The base theories of the discharge ignition in liquids are mentioned as well. Experiments were carried out in the reactor divided by the dielectric barrier (diaphragm) with a central pin-hole into two electrode spaces. Diaphragm was made of PET and the pin-hole initial diameter was 0.4 mm. Stainless steel electrodes were installed in the same distance of 2 cm from the barrier and symmetrically with respect to the diaphragm. Time resolved characteristics of current and voltage were recorded using two-channel oscilloscope which detected their output values. Parameters were measured by the constantly increasing DC voltage with a step of 50 V. When the regular discharge was ignited voltage had been gradually decreased. Used solutions contained sodium sulphate or sodium phosphate electrolyte at six different conductivities. Radiation emitted by the discharge was recorded by the spectrometer Jobin Yvon TRIAX 550. Emission spectra were investigated for one electrolyte at two different conductivities. The part with results presents all dependencies that were achieved during the measurements and all obtained data are compared. Recorded time resolved characteristics determine breakdown moment and describe current and voltage in particular parts within the static current-voltage curve. The work compares the influence of conductivity change on current-voltage characteristics as well as the effect of inorganic salt kind. By the conductivity enhancement the measured curve moves towards lower voltage which means that the breakdown voltage is decreased. Changing the inorganic salt the change of voltage related to the creation of bubbles in the diaphragm surroundings is observed. However, the change of electrolyte does not induce any significant change of the breakdown voltage. The last part of the work was focused on the optical emission spectroscopy of the discharge. Typical line system of OH radicals was identified in measured spectra which intensity was not dependent on the salt concentration. The work show particular processes taking place in the diaphragm surroundings when DC voltage is applied on the electrodes in electrolyte up to the diaphragm discharge ignition. Further, results describing the influence of conductivity and electrolyte changes on the processes are presented. The breakdown moment of the discharge and its dependence on the solution conductivity was determined. Optical emission spectroscopy revealed the contents of radiation emitted by the discharge.
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Study of sterilization effect of diaphragm discharge in liquids
Holíková, Lenka ; Slámová, Jitka (referee) ; Kozáková, Zdenka (advisor)
The main objective of this thesis is to study the sterilizing effect of diaphragm discharge in liquids. Sterilization is a process, which can eliminate all forms of life. Generally, sterilization is divided into physical and chemical methods. Plasma sterilization is ranked among physical methods although the action of chemical processes participates in the decontamination as well. Effects of UV radiation, free radicals and temperature are utilized in these methods. Fungi spores of Aspergillus niger F8189 and bacteria spores of Bacillus subtilis are selected as model organisms. Aspergillus niger microorganism is suitable for its resistance to changes in pH and it is viable in a wide range of pH values. Bacillus subtilis is chosen because of a good heat resistance. Diaphragm discharge is one of the possible types of electrical discharges in generated liquids. It is a low-temperature plasma, which is generated using a high DC voltage. In the created plasma streamers various physical and chemical processes rise. The chemical processes are mainly the generation of active species and particles that initiate subsequent chemical reactions and attack mould spores and bacteria in liquids. The physical processes include shock waves, strong electric field and ultraviolet radiation. Experiments were conducted in a reactor with separate cathode and anode space. In the dielectric barrier PET diaphragm with a pin-hole (initial diameter of 0.4 mm) was attached. Enlargement of the hole was observed as a result of degradation of material at the edge of holes due to the discharge. Degradation of spores was observed, depending on the time and on the input power. Other parameters measured were pH, conductivity and temperature. Experiments did not show any difference of discharge activity in the cathode and anode area. The main factor in the removal of spores Aspergillus niger was probably the temperature because no demonstrable effect of sterilization by the diaphragm discharge operation had been observed when heat resistant Bacillus subtilis was used. Also, it was made an attempt, which has been studied only the temperature effect of the fungi spores of Aspergillus niger. The samples were placed in a thermoregulator, where it was simulated the same temperature increase as at the discharge. The experiment had a similar course as an attempt at the discharge.
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Study of influence of organic dye structure on their decomposition in the diaphragm discharge in liquids
Pajurková, Jana ; Fasurová, Naděžda (referee) ; Kozáková, Zdenka (advisor)
The main goal of presented thesis is to study the influence of organic dyes structure on its degradation in diaphragm discharge in liquids. Diaphragm discharge is a kind of non-thermal plasma that can be generated in liquids by the application of high voltage. In plasma channels (so-called streamers), many physical and chemical processes are formed. High electrical field, shock waves and last but not least emission of electromagnetic waves in the range of visible and ultra-violet radiation appear among physical processes. The most important chemical process is generation of active species. These species initiate chemical reactions and could attack molecules of organic compounds contained in water solution. The reason why organic dyes were chosen in this study is its visible destruction, because it is related to its decolouration. Further, UV-VIS spectroscopy for the determination of concentration during the experiment can be used. Organic dyes are good models of organic substance often contained in waste water and for which removal classical biological, chemical and physical methods aren’t sufficient. Selected dyes were mostly from the group of azo-dyes: Acid Red 14, Acid Red 18, Acid Yellow 23, Direct Blue 53, Direct Red 79, Direct Red 80, Direct Yellow 29, Food Yellow 3 and further, Acid Blue 74 (indigotic dye) and Direct Blue 106 (oxazine dye). Experiments were carried out in a special batch discharge reactor with the anode and the cathode spaces divided by a non-conductive barrier, where the diaphragm with a pin-hole was placed. Measurement showed different removal in the anode and cathode space. We have supposed it was caused by different streamers features and energetic conditions. Dyes were decomposed with higher efficiency in the anode space where the final concentration reached 40 % of the initial concentration while it remained about 90 % in the cathode space. In this thesis the influence of dyes structure on the dye decomposition by electrical discharge was investigated. Dyes consisted of small molecules and dyes with many substitutes bounded on aromatic ring were decomposed more easily than dyes consisted of big molecules. The shift of characteristic wavelength on both directions (to shorter as well as longer wavelength) was observed during the experiments especially when the Direct dyes were decomposed. This phenomenon was probably due to the formation of intermediate product, which have different characteristic wavelength than the primary compound. In general, colourfulness is given by long conjugated systems of double bonds with substitutes bounded on an aromatic ring. Each change in the molecule structure provides the colour change and this could be the possible reason of the shift of characteristic wavelength. The other task was the comparison of degradation process efficiency by the mean of electrolysis and diaphragm discharge. Results showed that electrolysis (30 W) was more convenient for degradation of dyes consisted of small molecules while diaphragm discharge (130170 W) suited for complex molecules. For degradation of small molecules, oxidation on the anode assumed to be the most effective process that is initiated by electrolysis. For degradation of big molecules, attack of active species produced by the discharge is necessary.
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Study of electrolytic influence on organic dye decomposition in the diaphragm discharge in liquids
Davidová, Jaroslava ; Rašková, Zuzana (referee) ; Kozáková, Zdenka (advisor)
This Bachelor thesis is focused on study of chemical and physical influences which are proceed in diaphragm discharge in water solution. These processes could be used in water treatment. If DC non-pulsed voltage is applied, a significant influence of electrolysis must be taken into account. The main goal of this thesis is the estimation of electrolytic contribution to processes in the discharge. Theoretical part describes basic theory about creation of electrical discharges in water and electrolysis with emphasis on processes leading to destruction of organic compounds. Production of reactive particles (radicals, hydrogen peroxide, ozone, etc.) and electrochemical reactions on electrodes mainly belongs among these processes. This part describes analytical method (UV-VIS spectroscopy) which was used for determination of organic dyes concentration as well. Experimental part is oriented to experiment procedure which was carried out in an apparatus with separated anode and cathode area. Separation was made by dielectric diaphragm with a pinhole in the centre. Its initial diameter was 0.25 mm. Electrolytic decomposition was carried out at constant current of 30 mA and supplied power was about 14–32 W. Two Saturn dyes (Direct Blue 106 and Direct Red 79) were selected for experiments. As the decomposition was related to decoloration of the solution, UV-VIS spectroscopy in the range of 350–700 nm was used for determination of dye concentration. Next part focused on results presents various factors which had remarkable effect on decomposition of organic dyes. These factors were: various polarities of electrodes, conductivity and pH of solution, applied power, kind of electrolyte and structure of organic dye. The electrolysis had the significant influence on decomposition of small organic molecules. Decomposition was running mainly in the anode area where so called negative discharge was created. Optimal conditions were set by NaCl electrolyte with concentration providing initial conductivity of 500 S·cm-1. By the NaNO3 electrolyte half decomposition efficiency was achieved and in Na3PO4 electrolyte, the decomposition even didn’t run. The decomposition in the anode area was stimulated by the low pH value, which was decreasing during electrolysis. Generally, higher decomposition was achieved by the discharge than by pure electrolysis but the electrolysis had higher efficiency. In pure electrolysis, high rate of removal can be achieved by the application of a relatively low power. When bigger organic molecules were decomposed, the efficiency was higher by applying the discharge.
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