V. Golubeva

Publications

1 Study of Mordenite ZSM-5 and NaY Zeolites,Containing Cr, Cs, Zn, Ni, Co, Li, Mn, to Control Hydrocarbon Cold-Start Emission

Authors: V. Golubeva, A. Korableva, O. Anischenko, A. Nemova, N. Yegorushina, L. Kustov, G. Kapustin, U.S.Rohatgi

Abstract:

The implementation of Super-Ultra Low Emission Vehicle standards requires more efficient exhaust gas purification. To increase the efficiency of exhaust gas purification, an the adsorbent capable of holding hydrocarbons up to 250-300 ОС should be developed. The possibility to design such adsorbents by modification of zeolites of mordenite type, ZSM-5 and NaY, using different metals cations has been studied. It has been shown that introducing Cr, Cs, Zn, Ni, Co, Li, Mn in zeolites results in modification of the toluene TPD and toluene sorption capacity. 5%LiZSM-5 zeolite exhibits the most attractive TPD curve, with toluene desorption temperature ranging from 250 to 350ОС. The sorption capacity of 5%Li-ZSM-5 is 0.4 mmol/g. NaY zeolite has the highest sorption capacity, up to 2 mmol/g, and holds toluene up to 350ОС, but at 120ОС toluene desorption starts, which is not desirable, since the adsorbent of cold start hydrocarbons should retain them until 250-300ОС. Therefore 5%LiZSM-5 zeolite was found to be the most promising to control the cold-start hydrocarbon emissions among the samples studied.

Keywords: adsorbents, zeolites, Hydrocarbon emission control, temperature-programmed desorption

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Abstracts

1 Determination of Bromides, Chlorides and Fluorides in Case of Their Joint Presence in Ion-Conducting Electrolyte

Authors: V. Golubeva, O. Vakhnina, I. Konopkina, N. Gerasimova, N. Taturina, K. Zhogova

Abstract:

To improve chemical current sources, the ion-conducting electrolytes based on Li halides (LiCl-KCl, LiCl-LiBr-KBr, LiCl-LiBr-LiF) are developed. It is necessary to have chemical analytical methods for determination of halides to control the electrolytes technology. The methods of classical analytical chemistry are of interest, as they are characterized by high accuracy. Using these methods is a difficult task because halides have similar chemical properties. The objective of this work is to develop a titrimetric method for determining the content of bromides, chlorides, and fluorides in their joint presence in an ion-conducting electrolyte. In accordance with the developed method of analysis to determine fluorides, electrolyte sample is dissolved in diluted HCl acid; fluorides are titrated by La(NO₃)₃ solution with potentiometric indication of equivalence point, fluoride ion-selective electrode is used as sensor. Chlorides and bromides do not form a hardly soluble compound with La and do not interfere in result of analysis. To determine the bromides, the sample is dissolved in a diluted H₂SO₄ acid. The bromides are oxidized with a solution of KIO₃ to Br₂, which is removed from the reaction zone by boiling. Excess of KIO₃ is titrated by iodometric method. The content of bromides is calculated from the amount of KIO₃ spent on Br₂ oxidation. Chlorides and fluorides are not oxidized by KIO₃ and do not interfere in result of analysis. To determine the chlorides, the sample is dissolved in diluted HNO₃ acid and the total content of chlorides and bromides is determined by method of visual mercurometric titration with diphenylcarbazone indicator. Fluorides do not form a hardly soluble compound with mercury and do not interfere with determination. The content of chlorides is calculated taking into account the content of bromides in the sample of electrolyte. The validation of the developed analytical method was evaluated by analyzing internal reference material with known chlorides, bromides and fluorides content. The analytical method allows to determine chlorides, bromides and fluorides in case of their joint presence in ion-conducting electrolyte within the range and with relative total error (δ): for bromides from 60.0 to 65.0 %, δ = ± 2.1 %; for chlorides from 8.0 to 15.0 %, δ = ± 3.6 %; for fluorides from 5.0 to 8.0%, ± 1.5% . The analytical method allows to analyze electrolytes and mixtures that contain chlorides, bromides, fluorides of alkali metals and their mixtures (K, Na, Li).

Keywords: fluorides, bromides, chlorides, ion-conducting electrolyte

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