Wyniki wyszukiwania - BazTech

1

Kinetyka utleniania cyjanków za pomocą ozonu

Kępa U

Inżynieria i Ochrona Środowiska

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2012

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T. 15, nr 3

265--275

PL

Określenie kinetyki utleniania cyjanków za pomocą ozonu jest niezbędne dla skutecznego usuwania tego zanieczyszczenia w procesach uzdatniania wody. Badania prędkości utleniania cyjanków były prowadzone przez różnych naukowców, jednakże wyniki przez nich uzyskane nie były jednoznaczne. Wyznaczone rzędowości reakcji wahały się w zakresie wartości 0 do 2. Badacze nie byli również zgodni co do wpływu wartości odczynu na kinetykę procesu ozonowania. W niniejszej pracy określono kinetykę reakcji utlenienia cyjanków ozonem, wyznaczając rzędowości reakcji oraz obliczając wartość obserwowanej stałej szybkości reakcji. Opisano również wpływ wartości pH na przebieg procesu utlenienia, przyjmując pewne założenia upraszczające. Proces prowadzono w warunkach, jakie występują w trakcie uzdatniania wody w ciągu technologicznym stacji - przy stałym stężeniu ozonu w fazie wodnej. Stwierdzono, że dla badanych warunków proces utleniania przebiegał zgodnie z równaniem kinetyki pierwszego rzędu. Podobną rzędowość reakcji ustalono w badaniach Sondaka i Dodge’a oraz Balyanskiego. Wyznaczone równania funkcji f(t) = ln[CN] posłużyły do obliczenia obserwowanej stałej szybkości reakcji, której wartość zależna była od odczynu preparowanej wody. Wykazano, że dla pH = 9,0 kobs = 1,11•10−2, natomiast dla pH = 7,0 kobs = 1,39•10−3. Znaczne obniżenie wartości stałej kobs dla wody o niższym pH świadczy o tym, że na mechanizm utleniania cyjanków wpływała przede wszystkim forma, w jakiej występował ksenobiotyk. W miarę obniżania odczynu wody następował spadek stężenia jonów cyjankowych, natomiast wzrastała koncentracja cyjanowodoru. Z przeprowadzonych badań wynika, że główną rolę w utlenianiu cyjanków odgrywała reakcja ozonu z jonami cyjankowymi.

EN

Cyanides belong to substances which pose a serious health risk to people and other living organisms. Their appearance in water, even in low concentrations, has a very unfavourable effect on water environment. Ozonation is one of the methods which enables effective removal of cyanides from water. Ozone is one of the strongest oxidants. Due to the fact that it can be produced in large quantities and at competitive prices in comparison to chlorine and it decomposes to oxygen, ozone can be used to neutralize cyanides. In the process of oxidation no harmful by-products are produced, and the process shows high efficiency for high as well as low initial concentrations of cyanides. The determination of the kinetics of oxidation of cyanides to cyanates is necessary to achieve efficient ozonation of cyanides. This has been the subject of investigation of many authors. However, the data reported by different authors are not conclusive. The reported values of the reaction order range from 0 to 2 depending on the authors. Also, the researchers are not in agreement with one another as to the effect of the pH on the kinetics of the ozonation process. The main aim of this study was to determine the kinetics of the oxidation of cyanides using ozone. The scope of the study included the determination of the reaction order and calculation of the observed value of the reaction rate constant. The influence of pH on the oxidation process was also examined. The kinetics of the reaction was based on the rate of cyanides removal. For the determination of the kinetics of oxidation of cyanides with ozone some simplifying assumptions were made. The process was conducted under conditions typical for the water treatment in a technological cycle at a water treatment station with the constant concentration of ozone in the water phase. In the presented investigation the rates of removal of cyanides for the various initial concentrations were determined. The determination of the reaction order for cyanides ozonation was performed by using a graphic method. It was found that for the examined conditions of the process, oxidation followed the first-order equation. A similar order of reaction was determined in the research of Sondak and Dodge and Balyanski. The determined equations of the function f(t) = ln[CN] were used to calculate the observed value of the reaction rate constant, the value of which depended on the water pH. For pH = 9.0 kobs = 1.11•10-2whereas for pH = 7.0 kobs = 1.39•10-3. A significant de-crease in the value of the constant kobs proves that the mechanism of cyanate oxidation is influenced mostly by the form in which this contamination occurs. As the pH of water de-creases, a reduction of cyanide ions concentration takes place while the concentration of acidic forms of hydrogen cyanide increases. The conducted research shows that the reaction of ozone with cyanide ions plays the main part in cyanide oxidation.

2

Destructive oxidation of ethanol in the corona discharge reactor

Paterkowski W., Parus W., Kalisiak S.

Polish Journal of Chemical Technology

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2009

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Vol. 11, nr 4

57-62

EN

The results of investigation of ethanol destructive oxidation (model aliphatic alcohol) in a corona discharge reactor are presented. The process was performed at the temperature of 303 K in the corona discharge generator - the reactor system manufactured in our laboratory. The process temperature was kept constant by cooling down the reactor with a stream of air. The measurements were carried out using the following process parameters: the inlet ethanol concentration in the stream of gases in the range of 0.0028 to 0.132 mol/m3 (0.128 ÷ 6.086 g/m3), the gas flow velocity in the range of 0.15-0.33 m3/h (space velocity in the range of 1220 ÷ 2680 m3/(m3R źh)) and the power supply to the reactor ranged from 1.6 to 86.4 W. The active volume of the reactor was 1.23ź10-4 m3. The phenomenological method was applied for the description of the process. It was based on the assumptions that the reaction rate can be described by the first order equation in relation to the ethanol concentration and the design equation of flow tubular reactor can be applied for the description of corona reactor. The usefulness of this model was estimated using statistical methods for the analysis of the experimental results. The Statistica 6.0 software was used for this application. The first stage of this analysis showed the dependencies between the considered variables, whereas the second stage was to find the equations describing the influence of the selected process parameters on the rate of ethanol destruction. The parameters of A and B of apparent constant rate equation given in the form of Z = Aźexp(-B/P) were also determined. The results of the investigations indicated that the applied corona discharge generator - reactor system assures a high efficiency of purification of the air and industrial waste gases contaminated by ethanol. The ethanol destruction degree of αi = 0.9 was obtained at the power supply to the reactor amounting to 650 kW/m3R per unit of its active volume. The final products of the reaction were only the harmless carbon dioxide and water vapour. It has been stated that the rate of the destructive oxidation of ethanol reaction is well described by the first order equation in relation to the ethanol concentration. Under isothermal conditions, the reaction rate also depends on the power supply to the reactor. This dependence is well described by the empirical equation Z = 3,233źexp(-82,598/P). The obtained results also indicated that the method of destructive oxidation of ethanol in the corona discharge reactor can be useful for the removal of ethanol and probably other aliphatic alcohols from different gases. The described method of calculation of the real rate of the process can be successfully used in the design of corona discharge reactors applied for such processes.

3

Determination of the rate regime of the catalytic process of reducing of nitrogen oxide by means of ammonia on the active coke

Jastrząb K., Szarawara J.

Polish Journal of Chemical Technology

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2002

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Vol. 4, nr 3

13-17

EN

The paper presents the results of investigation concerning the determination of the rate of controlling the stage of the process reduction of nitrogen oxide by means of gaseous ammonia on the Polish active coke AKP-5. The influence of the scale factor, the grain diameter and temperature on the degree of the reduction of nitrogen oxide have been investigated. From the obtained results it is clear that the process takes place in the kinetic region and the optimum temperature of this process is 120°C. Apparent activation energy of reduction of nitrogen oxide on active coke has been calculated