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University of Patras

ΚΑΤΑΛΥΤΙΚΗ ΟΞΕΙΔΩΣΗ ΤΟΥ ΔΙΟΞΕΙΔΙΟΥ ΤΟΥ ΘΕΙΟΥ ΣΕ ΤΗΓΜΑΤΑ ΑΛΑΤΩΝ. ΣΧΗΜΑΤΙΣΜΟΣ ΚΡΥΣΤΑΛΛΙΚΩΝ ΕΝΩΣΕΩΝ ΚΑΙ ΑΠΕΝΕΡΓΟΠΟΙΗΣΗ ΤΟΥ ΚΑΤΑΛΥΤΗ

Abstract

dc:description

THE FORMATION OF LOW VALENCE CRYSTALLINE VANADIUM COMPOUNDS WAS STUDIED IN THE V2O5-M2S2O7 (M=NA, K, CS) UNSUPPORTED MELT SYSTEMS IN THE TEMPERATURE RANGE 350-480 C DURING SO2 OXIDATION WITH UNCONVERTED 10% SO2, 11% O2 AND 79% N2 AS THE FEED GAS. A GAS- MOLTEN SALT REACTOR SYSTEM WAS BUILT IN SUCH A WAY AS TO PROVIDE THE POSSIBILITY OF ISOLATING THE CRYSTALLINE PRECIPITATES UNDER OPERATING CONDITIONS AT ANY TEMPERATURE BY FILTERING THE CATALYST MELTS. BOTH V(IV) AND V(III) CRYSTALLINE COMPOUNDS WERE FORMED UNDER DIFFERENT PROCESS CONDITIONS. THE V(IV)-COMPOUNDS K4(VO)3(SO4)5, NA2VO(SO4)2 AND CS2(VO)2(SO4)3 AND V(III)- COMPOUNDS KV(SO4)2, NAV(SO4)2 AND CSV(SO4)2 WERE ISOLATED FROM THE MELTS. THE STRUCTURE OF THESE COMPOUNDS HAS BEEN DETERMINED BY X-RAY ANALYSIS. VIBRATIONAL SPECTRA (IR AND RAMAN) OF POLYCRYSTALLINE SAMPLES OF THE ISOLATED VANADIUM COMPLEXES HAVE BEEN RECORDED AND INTERPRETED. A BREAK IN THE ARRHENIUS TYPE PLOTS WAS OBSERVED AT TEMPERATURES WHERE THESE COMPOUNDS STARTED TO PRECIPITATE. FOR THE FIRST TIME IT HAS BEEN POSSIBLE TO OBSERVE THE DROP IN CATALYTIC ACTIVITY AND THE FORMATION OF LOW SOLUBLE VANADIUM COMPOUNDS SIMULTANEOUSLY. IT WAS ALSO FOUND THAT: (I) HIGH ALKALI TO VANADIUM RATIOS, LARGE ALKALI CATION PROMOTERS OR MIXING OF THE ALKALI PROMOTERS CAUSED THE PRECIPITATION AND THE STEEP ACTIVITY DROP TO OCCUR AT LOWER TEMPERATURES AND (II) THE CRYSTALLINE PRECIPITATES OF V(IV) AND V(III) COULD BE REDISOLVED BY A HEAT TREATMENT AT/OR ABOVE 470 C OR BY PURGING THE MELTS WITH N2. THE THERMAL STABILITY OF THE V(IV)-COMPOUNDS HAS BEEN INVESTIGATED BY MEANS OF DTA. FURTHERMORE THE DECOMPOSITION RATE OF KV(SO4)2 AND K4(VO)3(SO4)5 DURING ISOTHERMAL HEATING AT DIFFERENT TEMPERATURES IN THE RANGE 470-510 C HAS BEEN MEASURED AND IR SPECTRA OF THE DECOMPOSITION PRODUCTS HAVE BEEN RECORDED AND INTERPRETED. THE RESULTS INDICATE THAT A HEAT TREATMENT OF MELTS CONTAINING LARGE AMOUNTS OF V(IV) AND V(III) PRECIPITATES LEADS TO REOXIDATION OF VANADIUM IN THE +V OXIDATION STATE. CERTAIN CONDITIONS REQUIRED FOR REACTIVATION OF DEACTIVATED CATALYSTS ARE POINTED OUT AND ARE DISCUSSED IN RELATION TO THE DISOLUTION OF THE PRECIPITATES IN THE MELTS.

Degree

thesis:*
Grantor dc:publisher
University of Patras
Year dc:date
1990

Author and committee

dc:creator, dc:contributor.*
Author dc:creator
  • Μπογοσιάν, Σόγομων

Subjects

dc:subject × 14

Rights

Language dc:language
gre

Identifiers

dc:identifier.*
Identifier
10.12681/eadd/1227
OAI identifier oai:identifier
oai:10442/1227

Chain of custody

source
Harvested from
Greek National Archive of PhD Theses
Base URL
phdtheses.ekt.gr/eadd_oai/request
Last updated
2026-07-24
Source record
OAI-PMH GetRecord
citation

Μπογοσιάν, Σόγομων. ΚΑΤΑΛΥΤΙΚΗ ΟΞΕΙΔΩΣΗ ΤΟΥ ΔΙΟΞΕΙΔΙΟΥ ΤΟΥ ΘΕΙΟΥ ΣΕ ΤΗΓΜΑΤΑ ΑΛΑΤΩΝ. ΣΧΗΜΑΤΙΣΜΟΣ ΚΡΥΣΤΑΛΛΙΚΩΝ ΕΝΩΣΕΩΝ ΚΑΙ ΑΠΕΝΕΡΓΟΠΟΙΗΣΗ ΤΟΥ ΚΑΤΑΛΥΤΗ. University of Patras, 1990. http://hdl.handle.net/10442/hedi/1227